TW552415B - Electronic tongue as ozone detector - Google Patents

Abstract

An electronic tongue for the detection of ozone is based on voltammetry, and comprises at least one working electrode and a counter electrode, 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

552415 A7 B7 V. Description of the invention (1) The present invention relates to a detector often called an electronic tongue type, and particularly an electronic tongue based on electrochemical detection, for detecting the presence of ozone. And measure its concentration in the liquid sample. BACKGROUND OF THE INVENTION Ozone content control in the ppm range is an extremely important tool for the sterilization of substances, such as preparations, equipment and devices used in medical applications, in which ozone is used to eliminate harmful and unwanted species. Ozone is a substance with superior microbicidal entities such as viruses, bacteria, spores, and fungi. Since ozone is already toxic to these entities at low concentrations (ppm range), it is absolutely necessary to be able to control and measure ozone on the fly. This method is highly valuable for various types of equipment and procedures, such as medical devices, food and beverage processing equipment, and cleaning, disinfection, and sterilization in agricultural and feeding environments. This method can also be used to measure the oxidation of organic matter in the development and manufacturing of microelectronic products and manufacturing methods. Ozone detectors based on previous techniques have been based on a number of different methods. Most methods require the use of a reagent, which means that a sample must be taken from the system in which the ozone is to be measured, or we must accept the contamination of the system. The latter is unacceptable in terms of sterilization of water for medical purposes, for example. The spectroscopic method does not cause such interference, but requires a fairly complex system, which is expensive. Moreover, it needs to provide a window on the optical path, where blocking may occur over time, causing drift issues. In WO 99/13325, an electronic tongue based on an electric pulse according to a pulse program is disclosed. The pulse program includes a plurality of continuous pulses at different amplitudes, which are applied to an electrode. This electrical pulse is, for example, selected from the voltage pulse -4-This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 552415 A7 B7 V. Description of the invention (2) Impulse and current pulse. The obtained response signal is used as the input of a computer pattern recognition program for translation and output of the results, showing the desired sample properties, such as the concentration of the analyte, pH, etc. This analysis is based on a variety of methods, such as PCA (Principal Component Analysis). A brief calculation of PCA is shown in the paper by F Winquist et al. "Electronic Tongues Based on Voltammetry", Analytica Chimica Acta, 357 (1997) 21-31. This paper and the W0 Bulletin are in their entirety. It is hereby incorporated by reference. SUMMARY OF THE INVENTION The present inventor has now conceived a novel application of an electronic tongue of the type discussed above, which is used to measure the presence and concentration of ozone in a liquid sample. The invention is defined in item 1 of the scope of patent application. The electronic tongue of the invention is based on the voltammetry method and the specific choice of the metal or metal alloy of the working electrode. The advantages of the invention are, for example, systematic Convenience, which is long-term stable. Especially in a preferred embodiment, the system can be operated without a reference electrode. Therefore, any risk of electrolyte contamination by the reference electrode leakage of the system to be monitored is It is excluded. Moreover, the regular replacement of the reference electrode is exempted. Otherwise, such replacement must be completed at regular intervals, which further increases the overall cost. BRIEF DESCRIPTION OF THE DRAWINGS It is described in detail below with reference to the accompanying drawings, wherein FIG. 1 shows a typical experimental assembly for using the present invention; FIG. 2 shows a specific embodiment of a sensor device incorporating the concept of the present invention; and FIG. 3 shows that it can be used with the present invention. Pulse sequence; This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 552415 A7 B7 V. Description of invention (3) Figure 4 is a PCA chart of a typical ozone measurement method; Figure 5 shows The correlation between the measured and predicted concentration 値 measured by the present invention. Figures 6a-d are PCA charts of 値 measured with different single electrodes. Figure 7 is a four-electrode sensor with different metals as electrodes. PCA diagram of basic measurement; FIG. 8 shows an alternative embodiment of the sensor according to the present invention; FIG. 9 shows another embodiment of the sensor according to the present invention; and FIG. 10 is a schematic illustration of the sense of invention Implementation of the detector in a sterilizing device. Detailed description of preferred embodiments For the purposes of the present invention, the term "electronic tongue" is used to mean a device that includes at least one sensing element, which Back from the sample to be stimulation, Zhi-based processing method in a variable. "The sensing element" can be any one of many devices, such as, but not limited to, an electrode that undergoes a redox reaction on its surface. The invention will now be described with reference to a specific embodiment using a voltammetry system, and This type of assembly is shown in Figure 1. This assembly includes a sample reservoir 2 containing a sample, in which the ozone concentration is to be determined. This reservoir can be of a fixed type or designed as a flow cell, as described below In the experiment, a fixed cell with a magnetic stirrer 4 was used. The sensor device 6 was immersed in the sample liquid. A specific embodiment of the sensor device shown is shown in FIG. A rod-shaped carrier structure 8 in which many wires or needles 10 are embedded, the ends of which are exposed. The exposed ends of the wires constitute the working electrode 12 of the sensor device. The carrier structure is preferably made by Make sure metal _-jSj_ This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 552415

AT B7 V. Description of the invention (4) A very tightly sealed material between the wire and the material in which the wire is embedded to eliminate any interference caused by leakage of liquid between the carrier material and the wire during measurement. One suitable material is dental material sold under the trade names KompositTM, FiltekTM Z250, which is available from 3M Svenska AB, Sweden. Of course, any other material that provides the proper sealing capability can be used.

The Ag / AgCl (KC1 3M) electrode can be used as a reference electrode, but other conventional reference electrodes known to the skilled person can also be used well. The established metrics can be implemented in several ways. For example, a standard three-electrode system can be used, meaning a working electrode, an auxiliary (balanced) electrode, and a reference electrode. Alternatively, only the reference electrode and the working electrode can be used. However, it should be noted that the present invention operates extremely well without using any reference electrode at all. Therefore, in a preferred embodiment, two electrodes set up with a working electrode and an auxiliary electrode are used. Its potential is controlled electronically and / or using software in a control unit (eg potentiometer). In the specific embodiment shown (Fig. 2), the sensor device comprises six working electrodes 12 made of different metals. However, the number of electrodes is not important and can range from a single electrode to up to tens of electrodes, or even more. Its limit is set in principle only by the number of external connection points to be made. If hundreds of electrodes are to be connected to an external device, it becomes gradually difficult, but the possibility should not be ruled out. The metal used to make the electrode may be selected from one or more of the following groups, including Rh, Pt, Au, Os, Ru, Ni, Ti, Re, and alloys thereof, or alloys thereof with other metals. Any metal that produces the desired effect can of course be used. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 552415 A7 B7 V. Description of the invention (5) The metal wire extends through the entire carrier 8 and comes out at the opposite end, which is connected here To electric wires 14. A stainless steel tube system is used as the auxiliary electrode 16 (balance electrode), which is closely fitted to surround the rod-shaped carrier structure. If the equipment or system in which the present invention is implemented is itself made of, for example, stainless steel, the equipment housing can be used as a balanced electrode. Other materials for the auxiliary electrode are of course conceivable, such as Pt, Au. The electrical lead 18 is also connected to the auxiliary electrode. Electrical leads from all electrodes are connected to the potentiostat 20. The working electrodes are connected via the relay box 22 so that each working electrode is individually connected into a two-electrode type (without a reference electrode) or a three-electrode type (with a reference electrode). Current and current transient response are measured by a potentiostat MA 5410 (ISKRA, Chemel AB, Lund, Sweden) connected through the interface. An electronic filter with a time constant of 0.3 seconds is applied to the potentiostat to smooth the temporal response temporarily. Use a personal computer to control the system, such as the timing of the pulse deployment, the operation of the relay box, the temporary response of the measured current and the storage of data. -A computer program written in LabviewTM (National Instruments Corporation) is used to define the voltage applied to the electronic tongue, to control the sampling frequency, and to define the data points to be stored in the data matrix. For the experiments to be discussed below, the measurement sequence includes two types of voltages applied to the electronic tongue and two electrochemical cleaning procedures. Of course, it should be understood that this is just an example sequence, and in fact any combination of pulses (amplitude, duration, etc.) can be used as long as useful results can be obtained. Regarding the shape of the pulse, there are many options available, such as square / rectangular pulses (as in the examples below), sawtooth, sine wave, etc. Furthermore, a four-electrode (Au, Ir, Pt, Rh) sensor device is used. The order used in the experiment -8- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 552415 A7 B7

V. Description of the invention (6 is as follows (shown in Fig. 3): A: electrochemical cleaning% Zhu Shuo •, 丨 ~; 'book, start. Then, during .5 seconds, apply 2J volts: negative Note: 5 The two potentials are set to 0 volts in 2 seconds. For all operations, the last step. Repeat this step for the pen. B: Large Amplitude Pulse Voltammetry (LAP V) This LAPV program is applied during the second. a volt potential starts. Then, make the potential drop to: two working electrode seconds. Apply negative potential again, but set the potential again when the first potential = milliseconds. volt. Continue this sequence, Until reaching the final maximum potential of +2.1 volts. C: Electrochemical cleaning repeats the same procedure as in A. D: Step-wise voltammetry applies a potential of -2.1 volts to the working electrode, keeping this potential for "seconds" Then increase the single millivolts in sections until the final maximum potential of +21 volts is reached. Repeat this entire sequence AD for each of the sensor devices (meaning, four in the specific embodiment shown) working electrodes And is defined as a cycle. This metric Including sampling from the current 値 in the response curve due to the result of the potential pulse program. The measurement sequence is divided into 57 steps, each step has a duration of 500 亳 s. One step generates 500 counts, of which 19 are selected and stored

552415 A7 B7 V. Description of the invention (7) In the data matrix. The choice of data points can be adjusted for specific situations and is not critical to the method. It is only necessary to reduce the number of points to a reasonable number. However, a reasonable number may vary greatly from case to case. In some cases, four points may suffice, while in other cases a level of 100 points may be appropriate. Therefore, in the above example, each electrode will have 19 X 57 = 1083 numbers 値, which are stored in the matrix, and a total of 4332 metrics 全部 for all four electrodes are generated and stored. Data processing is accomplished by multivariable martingale analysis, especially using so-called principal component analysis, and will be briefly discussed below with reference to Figures 4-7. Therefore, for the example given above, where four different working electrodes are used, one measurement method involves performing a pulse sequence on each electrode, which results in a data matrix with 4332 numbers. Think of this matrix as a point in a 4332-dimensional space. Then, a new metric is implemented, which will generate a new matrix of 4332 numbers, and finally, a set of matrices representing many points in the 4332-dimensional space has been generated. In Table 1, a full data sampling experiment showing 147 measurements is shown, and it will be discussed in more detail, and Figure 4 is a graphical representation of the data in Table 1. -10- This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 552415 A7 B7 V. Description of invention (8) Table 1 Cycle 03 concentration (ppm) Temperature ° C Cycle 03 concentration (ppm) ) Temperature V Cycle 03 Concentration (ppm) Temperature ° C Cycle 0 Concentration (ppm) Temperature ° c 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, 〇, 2,9 32 100 2,90,0 31 147 2,9-3,0 32 7 1 〇31 54 3,0 -2,9 32 101 2,9-3,0 31 148 1 Γ〇31 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 MO 1 0 31 5Ί 3,0-2,9 32 104 2,0 31 151 11! Ο 31 58 2,5-1,9 32 105 31 152 12 Ιο 31 59 1,9-1,6 32 106 31 153 13 1 0,7-2,2 31 60 1,6-1,3 32 107 i, 5 31 154 14 1 2,2-2,6 31 61 Ι, Μ, Ο. 32 108 31 155 15 1 2,6-2,8 31 62 1,0-0,9 32 109 31 156 16 ί 2,9 31 63 0,9-0,8 32 110 1,2 31 157 17 j 2,9 31 64 0,8-0,7 32 111 31 158 18 1 31 65 〇, 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 〇, B 31 162 j ΊΊ 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 3 丨 165 25 3,0-2,9 32 72 0,4-0,3 32 119 31 166 26 3,0-2,9 32 73 〇, 3 32 120 31 167 27 3,0-2,9 32 74 〇, 3 32 121 〇, 5 31 168 1 2S 3,0-2,9 32 75 0,3-0,2 32 122 31 169 29 3,0-2,9 32 16 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 -11-This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 552415 A7 V. Invention Description 1 ( 9)! 1 [, Q 32 84 0 32 131 32 178 ί, Q 3,0-2,9 32 85 0 3 2 132 32 179 1 i jV ί Λ A 3,0-2.9 32 86 0 32 133 0 ,! 32 180 Ί I 4 (J! I! Λ〇-2,9 32 87 0 32 134 32 181, 4 1 ΓΤ ^ " 1 3,0-2,9 32 ~ 88 1,7-2,7 32 135 32 182! 42 i Ί ^ 3.0-2.9 32 89 2,7-2,9 32 136 0,1 32 183 丨 44 i |-3,0-2,9 (\ " Λ C \ 32 90 2,8-3,0 32 137 0,1-0 1 32 184 1 ^, 0-2,9 32 91 138 32 185 ii / 3.0-2,9 32 92 2,9-3,0 31 139 0,1-0 32 186! 46 3,0-2,9 32 93 31 140 0 32 187: "i-). 0 -2.9 32 94 1 2,9-3.0 31 141 〇32 188

Table 1 can be thought of as representing 147 points in the 4332-dimensional space. Applying PCA to this data 'involves finding the direction in which the data variability is greatest in this space. It will be a vector in 4332-dimensional space, called the first principal component PC1. Next is the largest variation in the direction orthogonal to the first principal component, which is of course also a vector, called the second principal component PC2 (the other principal components can be calculated until most observations are explained) ). A new matrix is then formed, as defined by the main components, and the data set is reduced considerably, depending on the importance of the main components. In many cases, this reduction will reach only two dimensions. Therefore, the two vectors PC1 and PC2 define the quadratic plane, which maximizes the variation in the original observation. Now project 147 points in the approximate space to the plane spanned by PC1 and ㈣. So the chart is shown. μ T% During the measurement sequence, this system is modified from the perspective of ozone concentration. Whether it is by actively increasing the concentration with an ozone generator, the oxygen decays over time and decays. Table i clearly illustrates this change. Chen = due to odor. In the circulation suppression, its concentration is 0 ppm. In the purchase of 8, its system = one by one.

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Plus' and the tension of 7 gram during cycle 22-57 stayed at about 3 PPm. The concentration was then attenuated in cycle # 58-81 to 0 ppm during cycle # 82-87. Once again, the concentration of radon in Xunyi # 88 91 increased to reach the period during which the ## was taken off, then the spoon was drunk and then decayed (# 103] 39). The increase in concentration was generated in # 142-147. As can be seen, the measure can be subdivided into several groups that are related to different states of the system, such as different concentrations and concentration decay cycles. Figure 4 (The chart-based measurement method is used to establish a data analysis model for ozone concentration. When this model is applied to a set of measurements on a system with unknown ozone concentration, a prediction of the concentration can be performed. To confirm that this model works, make a chart of predictions versus known ones. Such a chart is shown in FIG. 5. As can be seen, the relationship between puppets is extremely good. In Figures 6a-d, it is shown that the PCA chart is used to measure 値 on a set of individual electrodes of four different metals (Au, Pt ·, Ir, Shan) using the above pulse sequence AD, and will be briefly Discussed below. As can be clearly seen, there is a qualitative difference between the experiments. The most obvious graph of R representing Rh (Figure 6d) has a significantly larger deviation in the Υ direction than the others. This deviation can be used for modeling purposes, and especially for the determination of ozone concentration. & In a further experiment shown in Figure 7, this chart contains data from all four electrode metrics. It can be seen that the electrode system made from Rh is the main contributor to this curve. If a model is made on the basis of "training data," and it is measured using a sensor with different metals, it has been proven that although it is from a lesser, -13-

This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 552415 A7 B7 V. Description of the invention (11) Ozone-specific π metal (Au, Ir, Pt in the above example) has a great contribution Small, but it proves that the overall performance of this four-electrode sensor is better than a sensor with a single Rh electrode. This better performance is reflected in the better correlation coefficient in the corresponding PLS chart. One explanation is that in the data reduction process inherent in PCA, any "white nose" in the data does not contribute, but rather any valid information, regardless of its amount, will have a positive contribution, and the final result will be improved accordingly In the measurement method discussed above, in the pulse sequence, the "electricity" bit is changed between-2.1 V and +2.1 V. However, other measurement intervals may be selected, and we may make the scan The interval is optimized. In particular, it is possible to work only in the negative range, for example 0 to -3.0 volts, because the redox potential of the possible reactions involving ozone is on the negative side. The quality of the results is relatively important because the higher the conductivity, the better the measurement of 値. Therefore, you may generally want to measure the conductivity-in order to be able to adjust it by adding ionic species if the system allows it. For a closed line system, most of them are not feasible and sometimes undesirable, especially in killing In the bacterial system, 0, regarding the conductivity measurement, two additional electrodes can be provided on the same carrier near the working electrode of the electronic tongue. As a specific embodiment of the sensor device as discussed above, only the working electrode One of the many possible forms. Another way of making a device with multiple electrodes is shown diagrammatically in Figure 8 and is obtained by providing a laminate, such as a planar carrier member of ceramic or other inert material 24 Parallel strips of different metals have been deposited on it 26. If one edge of this laminate is immersed -14- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 552415 A7 B7 V. Description of the invention (12) is not in a medium containing ozone, so that a part of each metal strip is in contact with the medium, then the other end of each strip can be similar to the rod sensor device as pointed out above Way, another design of the sensor device connected to the potentiostat and the sensor device is shown diagrammatically in Figure 9, The electrode strip 28 in the wall of the tube segment 30 is integrated as part of the circulation conduit for, for example, sterilization. These metal strips can be embedded in the wall of the special tube segment and have electrical connection points 32, at least in each One end of the strip to provide connection to appropriate peripheral equipment, such as potentiostat. The skilled person can set up several other variants and modifications of the actual configuration and type of electrodes for the sensor device according to the invention, all of which All are intended to fall within the scope of the patent application attached herewith. One of the great advantages of the detector and measurement system according to the present invention is that it is suitable for, for example, the connection of ozone in sterilization or purification equipment > Among them is the need to prevent pollution. In Fig. 10, a schematic diagram of such an application is shown. 0-Therefore, the purification system shown includes a processing chamber 34 which may be a chamber containing a device to be sterilized, such as a surgical instrument, or it may itself Contains a device such as a dialysis device or the like. A feed conduit 36 having an inlet 38 is hermetically connected to the chamber. The outlet duct 40 transports used ozone-containing gas or liquid for disposal. In some applications, Evening Fire 9 can be recirculated back to the feed duct (not shown). According to the ozone sensor 42 and 44 of the invention, the control unit 46 can be connected to control the sensor and respond to its output, to determine when the desired level such as the degree of sterilization has been achieved and, if necessary, to adjust the ozone content in the feed. Therefore, as shown, J can implement the present invention as an ozone detection system. Y -15- This paper size applies the Chinese National Standard (CNS) A4 specification (210 x 297 mm) 552415 A7

&amp; It is connected to or on the spring in the liquid circulation system where the ozone concentration is monitored. This system is based on voltammetry and i includes at least one working electrode, which is made from the materials as mentioned above in the discussion of the sensor device and the balance wrap. These electrodes are connected to a programmable pulse generator, which is capable of applying the power pulses in the 敎 sequence to the working electrodes, one at a time. The system further includes a recording device for recording the output from the working electrode in response to the applied pulse sequence. A sampling device is provided to sample the output silk at predetermined intervals, and the sampled data is stored in a matrix in a 'memory body'. There is a processing unit for performing the data matrix <variable martingale analysis>, and a display device for displaying a result of the multivariable martingale analysis. Calibration curve To study the drift on the built-in ammeter sensor in the ozone generator, 13 calibration experiments were performed during this work. Three (four for the calibration curve) individual measurements form the basis of a calibration curve. Select a multi-point operating curve with 3 repeats and a wavelength of 260 nm. The standard samples included deionized water with an ozone level of 1, 1.5, 2 and 3 ppm. Use deionized water as the reference solution. See the table and figure below for details. i Spectrophotometric determination of the quantity and calibration curve nr 1,000 000 〇 03 concentration (浓度 m) 1 Abs 2 Abs 3 Abs 4 Abs MW Abs 1 0,066 "0,059 0,06 [0,065 bu 0,063 1,5 0,091 0,084 0,09 0,087 0,088 2 0,128 0,113 0,113 ί 0,13 0,121 3 0,186 0,164 0,164 0,191 0,176 -16- This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) 552415 A7 B7 V. Description of the invention ( 14) y = 0.059x + 0.0028 correlation coefficient = 99.73% calibration curve nr 2, 000925 〇3 concentration (ppm) 1 Abs 2 Abs 3 Abs MW Abs 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 A176 y = 0.057x + 0.0048 Correlation coefficient 99.99% Calibration curve nr 3, 001011 03 Concentration (ppm) 1 Abs 2 Abs 3 Abs MW Abs 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 Correlation coefficient 99.90% Calibration curve nr 4, 001108-03 Concentration (ppm) 1 Abs 2 Abs 3 Abs MW Abs 1 0,068 0,068 0,063 0,066 1 , 5 0,102 Π 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 = 0.059x4-0.0087 Phase ratio 99.92% Calibration curve nr 5, 001206 03 Concentration (ppm) 1 Abs 2 Abs 3 Abs MW Abs 1 0,071 0,064 0,076 0,070 1,5 0,088 0,091 0,091 0,09 0 2 0,114 0,123 0,124 0,120 3 0,166 0,168 0 丄 180 0,171 -17- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 552415 A7 B7 V. Description of the invention (15) y = 0 · 051χ + 0.017 Correlation coefficient 99.83% The measurement sequence (refer to the figure below) consists of two voltage types (obtained from Labview of National Instruments) and two electrochemical cleaning procedures, which are applied to electronic tongues in the following order: 1) electrification Learn the cleaning procedure The electrochemical cleaning procedure of the electrode was started in 0.5 seconds and started with a positive voltage of 1.5 volts. A negative potential of 1.5 volts was then applied for the same time. Then, set the voltage to 0 volts for 2 seconds.

2) LAPV LAPV starts at a potential of -2.1 Volts, and then sets the voltage to 0 Volts. Then, increase the potential by 300 millivolts and start the sequence again from the beginning. This is continued until the voltage reaches a final maximum potential of +2.1 volts. 3) Electrochemical cleaning procedure See 1) above. 4) Stepped voltage starts at -2.1 volts and then increases by 300 millivolts until the final maximum potential is reached. -18- This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 552415

2,1 Π Π

τ Figure 5.4. Applied voltage The order of ^ 2 is applied to gold wire first, followed by sensitization, reduction of silk, j and boundary. One cycle. The metric sequence is divided into 57 steps, each with 500. \ 、 Step time. The current is sampled at a sample frequency of 1000 Hz. ^ Busao produced 500 samples (keys). Nineteen of them were stored in the data matrix on each working electrode. 19 X 57 = 1083 numbers were stored in the data matrix. From all four working electrodes, 4 X 1083 = 4332 measurements are generated. The selected applied potential, sampling frequency, and data points are shown in the table below. The number of cycles of film measurement: 200 ^ Time between cycles: 0 minutes Number of probes: 4 Samples / steps: 495 Acquisition rate: 1000 samples / s Steps: 57 Step time · 500 milliseconds Keys: 19 Data points / ranks: 4332 This paper size is in accordance with Chinese National Standard (CNS) A4 specification (21 × 297 mm) 552415 A7 B7 V. Description of the invention (17 1 Output data output data key number 1,500 "1,500 25 Ί, 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 1 300 • 1,200 -1,500 325 0,000 -1,200 f 350 -0,900 -0,900 375 0,000 -0,600 400 -0,600 -0,300 Γ425 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 Ozone concentration during the experiment. In the experiment, change manually at 0-3 ppm. Then, use the automatic program to change the ozone concentration. The ozone concentration and its phase The temperature is recorded manually and automatically for each cycle during the measurement period. In the six starting experiments, the impact of cold to warm ozone generator, water quality, old to new seal ring and conductivity was studied. Please refer to the experimental data in Table 5.1 below. For more detailed experimental data, please refer to the following table and figures. 20- // ^ ΛΤ〇 \ Λ iiL / ΟΙ Π X) 552415 A7 B7 V. Description of the invention (18) 000919 measurement record:

In experiment 1, new deionized water (just before the start), seal ring nr 丨 and cold ozone generator were used.

Loading line * Ozone concentration is changed manually after the indicated cycle. ^ y # μ 八 Every third cycle (1, 4, 7, etc.) and data points obtained from electrochemical cleanup are excluded from the sputum. _________- 21 -____— ^^^ The silver scale of this paper applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) 552415 A7 B7 5. Description of the invention (19), ingredient 2 (2.3%)

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V. Description of the invention (20) Tongue 000920 Tang Jizhi Green Ionized water (just before warming), sealing ring nrl, and Wenzhi Shifa% 〇3 concentration (PPm)

The ozone concentration was changed manually after the indicated cycle. Every third cycle (1, 4, 7, etc.) and data points obtained from electrochemical cleanup were excluded from data analysis. ______- 23- This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 552415 A7 B7 V. Description of the invention (21) 丨 2.00 丨 Ibo ingredient 2 (2.4%) οb ο lbo NJb 〇 service 芩One (68.70 / 0)

This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -24- 552415 A7 B7 V. Description of the invention (22) Record new millimeter water with electronic tongue 000926 (just before warming) And before), sealing ring nr 1 and warm ozone generator, used for test 4. Cycle 03 concentration (ppm) Temperature ° C Cycle concentration (ppm) Temperature ° C Cycle 03 concentration (ppm) Temperature ° C 1 〇34 45 89 2 〇34 46 90 3 〇34 47 91 4 〇34 48 92 5 〇 34 49 93 2,9-3,0 32 6 〇34 50 94 2,5-2,1 32 7 〇34 51 95 2,1-1,6 32 8 〇34 52 96 1,6-1,3 32 9 〇34 53 97 1,0-0,8 32 10 〇34 54 98 0,8-0,7 32 11 〇34 55 99 0,7-0,6 32 12 * 〇34 56 32 100 〇, 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 1 16 2,0-2,3 33 60 104 0,2-0,1 32 I 17 2,3 33 61 105 0,1 32! 18 2,3-2, 4 33 62 106 Ο, ΙΌ 32 1 19 2,4-2,5 33 63 107 〇32 20 2,5 33 64 108 〇32 21 2,6 33 65 109 〇32 22 66 110 〇32 23 2,7 33 67 111 〇32 24 2,7 33 68 112 〇32 25 69 113 〇32! 26 70 114 * 〇32 27 71 115 0,7-0,9 -32 28 72 * 〇32 116 ◦, 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 ΊΊ 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, 〇32 * Ozone concentration is after the indicated cycle, manually change. Every third cycle (1, 4, 7, etc.) and data points obtained from electrochemical cleanup were excluded from data analysis. -25- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 552415 A7 B7

This paper size applies to China National Standard (CNS) A4 (210x 297 mm) 552415 A7 B7

552415 A7 B7

Order k-

Hold

552415 A7 B7 V. Description of the invention (26 Q ^

-8.8 • 9.7 .5.2 -0.7 .ingredient 1 (62.5%) 3.9 8.4 -29-

This paper size applies the Chinese National Standard (CNS) A4 specification (210 x 297 mm) 552415 A7 B7 V. Description of the invention (27 Record new millimeter of water measured by electronic tongue 001002 (before warming and before beginning) Used in Experiment 6. Conductivity measurement was also performed on the sealing ring nr2 and the warm ozone generator, which were circulated. 0 concentration (ppm) temperature cycle 0 concentration (Ppm) temperature ° c cycle 0 concentration (ppm) temperature ° C : 1 〇32 44 0,4-0,3 32 88 1,2-2,6 26; 2 〇32 45 0,4-0,3 32 89 2,6-3,0 26 3 〇32 46 〇, 3 32 90 2,9-3,0 26 Cond 2,4 uS 47 〇, 3 32 91 2,9-3,0 26 ί 4 〇32 48 0,2-0,3 32 92 2,9-3, 0 26 丨 5 「〇32 49 0,2 32 93 26 丨 β 本 〇32 50 0,2 32 94 Ί 0,3-1,2 32 51 0,2-0,1 32 95 I 8 1,2- 2,3 32 Cond 7,9 nS 96 ί 9 2,3-2,7 32 52 0,1 32 97: 10 2,8-2,9 32 53 〇, 1 32 98 2,9-3,0 26 I 11 2,9 32 54 99 i 12 2,9-3,0 32 55 100 丨 Cond 3,9 "S 56 101 丨 13 2,9-3,0 32 57 102 2,9-3,0 26 14 2,9-3,0 32 I 58 Cond 8,2 uS 15 1 2,9-3,0 32 59 103; 16 2,9-3,0 32 60 1 04 17 2,9-3,0 32 61 105 26 *! 18 2,9-3,0 32 62 106 丨 19 5,8) aS 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 i 23 1,8-1,5 32 67 Cond 9,4 uS 丨24 1 &gt; 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 1 Cond 7,9 uS 72 115 26 '28 0,9 32 73 116 26 1 29 0,9 32 74 117 26! 30 0,8 32 75 118 26 ί 31 0,8-0,7 32 76 119 1,7-1,6 26; 32 0,7 32 77 120 1,6-1,5 26 1 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 丨 38 0,5 32 83 126 1,2 26 39 0,5 32 84 127 ί 40 0,5-0,4 32 85 128 41 0,4 32 86 129 1,0; 42 0,4 32 87 * 130! 43 〇,. 32 Cond 5,1 yS 131 0,9 26 -30 This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 public love) 552415 A7 B7 V. Description of the invention (28) Cycle 03 concentration (ppm) Temperature ac Cycle concentration (p pm) Temperature cycle 0;} Concentration (ppm) Temperature ° C 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 〇, 4 25 * The ozone concentration is changed manually after the indicated cycle.

Cond = conductivity Every third cycle (1, 4, 7, etc.) and data points obtained from electrochemical cleanup are excluded from data analysis. -31-This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) 552415 A7 B7 V. Description of the invention (29) ‘η (ο / or inch) (N ^^ .0ο 3 〇

-6.0 8.0 • 5.0 -1 --- -2.0 Ingredient 1 (58.0%) 1.0 4.0 -32-

This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 552415 A7 B7 30 V. Description of the invention (recording the new millimeter water (just before the start) measured by the strip 001013), seal ring nr2 and Cold ozone generator for experiment 7

The f concentration changes automatically, see the table below. ϊίίίΙΊ1,4'7, etc.) (not included in the table above), with ozone concentration differences exceeding ο.1 ppm (&gt; &amp; 未 I 3 in the table above) and data points obtained from electrochemical cleanup, are Excluded in the data points 33-552415 A7 B7 V. Description of the invention (31) Automatic program of ozone generator: 〇3 concentration time (PPm) (minutes) 〇30 ~ 3 60 〇60 3 60 〇 ^ 60 3 60 ~ 1 1 60 2 60 | T ~ 60 -34- This paper size applies to China National Standard (CNS) A4 (210X297mm) binding

Line 552415 A7 B7 32 V. Description of the invention -1.00 t -190 Composition 2 (4.8%) 〇 Γ〇 b b ο 〇 ο ο 3.0〇 -5.0 Ob 5.0 · Rammer 1 (92.10 / 0)

-35- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 x 297 mm) 552415 A7 B7 V. Description of the invention (33) Record new millimeter water with electronic tongue 001014 (just before the start) , Seal ring nr2 and cold ozone generator, used in experiment 8. 0% concentration (ppm) Temperature ° C Cycle 03 concentration (PPm) Temperature · ° C Cycle concentration (ppm) Temperature ac 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 丨 6 〇, 〇5 21,5 78 3,02 [31,8 152 2, 〇〇32,8 I 8 0, 05 21,5 80 3,00 31,8 153 2,02 32,8 ί 9 0,05 21,5 92 0,70 31,8 155 2,01 32,8-ί 11 0,06 21,5 96 0,41 31,8 158 1,97 32,8! 12 〇, 〇7 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 ί 48 0,99 25,7 113 2,98 32,8 165 2,00 32,8 1 50 〇, 9〇25,7 114 3,00 32,8 167 2,00 32,8: 51 Γ 0 , 81 25 &quot; 116 2,95 32,8 168 「1,99 32,8 丨 53 1 0,72 25,7 117 2,98 32,8 173 3,03 32,8 1 54 0,64 25,7 119 2,96 32,8 176 3,00 32,8 1 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, 〇3 32,8 i 69 2 , 95 30,8 140 0,99 32,8 188 2,96 32,8 i 71 2,98 30,8 143 0,98 32,8! 72 2,96 30,8 144 1,00 32,8 Ozone The concentration is changed automatically, see Appendix 9. Every third cycle (1, 4, 7, etc.) (not included in the table above), a cycle with a difference in ozone concentration exceeding 0.1 ppm (not included in the table above) and data points obtained from electrochemical cleaning, Departments are excluded from data analysis. -36- This paper size applies to China National Standard (CNS) A4 (210X297 mm) 552415 A7 B7

〇 b This paper size applies to China National Standard (CNS) Α4 size (210 x 297 mm) -37-

Claims (1)

552415 Patent No. 0990m363_Please file A BCD 552415 Patent Application No. 090131363 Chinese Patent Application Replacement (May 1992) VI. Patent Application Auxiliary electrode for measuring conductivity. 10. For the electronic tongue of the scope of patent application item 1, 2 or 3, wherein the working electrode is made from Rh. 11. A voltammetry-based ozone detection system for detecting the presence and / or concentration of ozone in a liquid sample, comprising at least one working electrode (12), made of one or more transition metals or Au, or an alloy thereof, or an alloy thereof with other metals; a balance electrode (16), a programmable pulse generator (20), which can apply a predetermined sequence of power supply pulses to the working electrode (12); a recording device, with The output from the working electrode is recorded in response to the sequence of applied pulses; a sampling device is used to sample the output value at a predetermined interval; a memory is used to store the sampled value in a matrix; a processing unit ( PC) for performing multivariable value analysis of the data matrix; and a display device for displaying results of the multivariate value analysis. 12. For the ozone detection system under the scope of patent application item 11, wherein the working electrode is made from Rh. 13. For the ozone detection system with the scope of claims 11 or 12, the electrode is provided in the processing equipment in a connected manner. -2- This paper size applies to China National Standard (CNS) A4 (210 x 297 mm)