• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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  • 法律状态
  • 优先权
    • 专利摘要:
    Sensor, probe and equipment for the measurement of soluble oxygen chemical demand based on amperometric detection for water quality control applications. Sensor (1), probe (10) incorporating said sensor and equipment (20) that incorporates the probe for the measurement of soluble oxygen chemical demand based on amperometric detection for water quality control applications, the sensor being provided with a external metal surface intended to be immersed in a water sample, comprising a layer of a composite material of multi-wall carbon nanotubes and polystyrene and an inorganic catalyst, the inorganic catalyst being preferably a nano-powder of cuo and ago. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2595114A1
    申请号:ES201530917
    申请日:2015-06-26
    公开日:2016-12-27
    发明作者:César Fernández Sánchez；Manuel Gutiérrez Capitán；Antonio Baldi Coll；Cecilia JIMÉNEZ JORQUE；Raquel GÓMEZ GUTIÉRREZ；Jordi Cros Herrero；Virginia GARCÍA DEL PUERTO
    申请人:Adasa Sist S A U；Adasa Sistemas Sau；
    IPC主号:
    专利说明:

    Sensor, probe and equipment for chemical demand measurement of soluble oxygen based on amperometric detection for water quality control applications
    5Technical sector of the invention
    The sensor, probe and equipment for the measurement of chemical demand of soluble oxygen based on amperometric detection is useful for performing quality control of wastewater
    10 treated and untreated.
    Background of the invention
    The chemical oxygen demand is a useful parameter to measure the degree of contamination
    15 of the water from the amount of substances that can be oxidized by chemical means that are dissolved or suspended in a liquid sample and is expressed in milligrams of diatomic oxygen per liter (mgO2 / l).
    This parameter is usually monitored in inland waters (rivers, lakes or aquifers),
    20 sewage, rainwater or water from any other source that may contain an appreciable amount of organic matter.
    The chemical oxygen demand varies depending on the characteristics of the materials present, their respective proportions, their oxidation possibilities and other
    25 variables This is why the reproducibility of the results and their interpretation cannot be satisfied except in well defined and strictly respected test methodology conditions.
    There is therefore a need to measure, preferably automatically, the demand
    30 oxygen chemistry in treated and untreated wastewater. In addition, in the case of untreated water, these are characterized by high turbidity that does not allow the use of traditional measurement technologies, such as colorimetry or spectroscopy, without prior filtration of the sample.
    35 It is therefore an objective of the present invention to disclose a sensor that allows measuring


    the chemical oxygen demand without having to previously filter the samples to be analyzed, and which in turn requires a reduced consumption of reagents, being able to give acceptable values in situations where the concentrations of the chemical oxygen demand are not regularly elevated but given in a timely manner.
    5It is another objective of the present invention to disclose a probe incorporating said sensorand a device that incorporates the probe and allows to detect a high range of values ofChemical oxygen demand, regardless of the turbidity of the sample.
    It is another objective of the present invention to disclose a device that incorporates said probe and allows automatic measurements of chemical oxygen demand to monitor water contamination.
    Explanation of the invention.
    The sensor for the measurement of chemical demand of soluble oxygen based on amperometric detection for water quality control applications of the present invention is those with an external metal surface intended to be submerged in a water sample, the surface comprising metallic a layer of composite material, known
    20 also as a resin, of multipared carbon nanotubes and polystyrene.
    In essence, the sensor is characterized in that the composite material layer also comprises an inorganic catalyst that assists in the oxidation of the organic matter present in the water sample in order to determine the chemical oxygen demand measurement
    25 by amperometric detection of the electric current generated in said composite material.
    In a variant of interest, the material comprises 6% inorganic catalyst, which in a preferred variant is a nano-powder of dimensions around the micrometer, CuO and
    30 AgO, the material preferably comprising 5.9% CuO and 0.1% AgO as inorganic catalyst.
    According to another aspect of the invention, the material comprises 13.4% of multipared carbon nanotubes and 80.6% of polystyrene


    In a variant embodiment, the external surface of the sensor is flat, metallic or of any other electrically conductive material and has an area of 9 mm2.
    The use of a sensor like the one described above is also described in the present invention.
    5 described for the measurement of chemical demand of soluble oxygen based on amperometric detection for water quality control applications, since said sensor will emit a faradaic current under certain conditions that will be proportional to the chemical oxygen demand of the medium with which it is in contact, preferably a liquid medium such as a water sample.
    The method of manufacturing the sensor of the present invention comprises the steps of preparing a suspension of solids comprising carbon nanotubes, polystyrene and an inorganic catalyst in an organic solvent; deposit the suspension on a metal surface of a sensor; and remove the solvent from the suspension by drying at a temperature
    15 less than 100 degrees Celsius, resulting in a layer of composite material, such as a resin, formed on the metal surface. For example, the solvent may be an organic solvent, preferably toluene.
    In a variant embodiment, in the manufacturing process 6% of the solids of the suspension are an inorganic catalyst.
    It is further disclosed that the inorganic catalyst of the solids of the suspension of the manufacturing process comprises a nano-powder, of dimensions of the order of micrometers, of CuO and AgO, preferably the solids of the suspension comprise 5.9%
    25 CuO and 0.1% AgO.
    In a variant of interest, the solids of the suspension comprise 13.4% of multipared carbon nanotubes and 80.6% of polystyrene
    A probe for the chemical demand of soluble oxygen based on amperometric detection for water quality control applications comprising a working electrode which is the sensor of the present invention is also disclosed in the present invention.
    In one variant embodiment, the probe further comprises a reference electrode and a


    Auxiliary electrode integrated in the same probe forming a compact package, preferably protected by an outer shell.
    Preferably, the working electrode of the probe will be encapsulated in a printed circuit board provided with a connector for connection with a measuring device. Naturally, if the probe also incorporates a reference electrode and an auxiliary electrode, all of them can be encapsulated in the same printed circuit board, or in several adjacent plates, so that they can be easily connected to the same measuring equipment, such as a potentiostat, to perform the voltammetric analysis. It is also envisaged that the reference and auxiliary electrodes are covered with a polymeric membrane to keep them clean when they come into contact, for example, with wastewater from which it is desired to analyze the chemical demand for soluble oxygen.
    In a variant of interest, the working electrode, the reference electrode and the auxiliary electrode are encapsulated in a printed circuit board provided with a connector for connection with measuring means.
    A method for the chemical demand measurement of soluble oxygen based on amperometric detection for water quality control applications in a water sample is also disclosed by means of a probe provided with a working electrode formed by the sensor of the present invention. , a reference electrode and an auxiliary electrode, the working, reference and auxiliary electrodes being immersed in the water sample forming an electrochemical cell, comprising the steps of adding a basic solution to the water sample until the pH of the sample of water reaches a pH of 12; apply an activation potential between +0.4 and +0.7 V between the working electrode and the reference electrode; detect the faradaic current generated in the working electrode when applying the activation potential, which is directly proportional to the chemical oxygen demand of the water sample in which they are submerged, and apply an algorithm corresponding to a model previously obtained by analysis PLS to detect the chemical oxygen demand of the water sample. Thus, the potential of the working electrode can be measured in relation to the reference electrode, and the auxiliary electrode will allow the current of the working electrode to pass, so that it can be measured. This three electrode system is known in the analytical chemistry technique called voltamperiometry.
    In a variant embodiment, the activation potential is + 0.6V, allowing a better


    detection of the chemical demand value of soluble oxygen in the water sample.
    A device for measuring chemical demand for soluble oxygen based on amperometric detection for water quality control applications comprising a cuvette for housing a water sample is also disclosed; a probe with a working electrode formed by the sensor of the present invention; a reference electrode and an auxiliary electrode that may preferably be integrated in the probe; means for adding a base solution to the cuvette; means for adding a standard solution to the cuvette; means for adding a cleaning solution to the cuvette; means for recirculating the water sample in the bucket; means for filling a sample of water in the bucket; and a means for emptying the cuvette, the working electrode, the reference electrode and auxiliary electrode being adapted to be immersed in the sample of water housed in the cuvette and connected to measuring means, preferably formed by a potentiostat, being the equipment controlled by control means such as a computer.
    Brief description of the drawings
    To complement the description that is being made and in order to facilitate theunderstanding of the features of the invention, is attached hereindescriptive a set of drawings in which, for illustrative and non-limiting purposes,represented the following:
    Fig. 1 shows a schematic view of the sensor of the present invention;Fig. 2 shows a sectional view of the sensor of Fig. 1 along axis aa;Fig. 3 shows an enlarged image of the composite material of the sensor of Fig. 1;Fig. 4 shows a probe incorporating the sensor of the present invention;Fig. 5 shows cyclic voltamperograms registered with the sensor for differentglucose concentrations;Fig. 6 shows chronoamperograms registered with the sensor for differentglucose concentrations;Fig. 7 shows the sensor calibration curve obtained from the chronoamperogram ofFig. 6 for an activation potential of 0.6V; YFig. 8 shows a device incorporating the probe of Fig. 4.


    Detailed description of the drawings
    Figs. 1 and 2 show a schematic view of an embodiment variant of the sensor 1 of the present invention for the measurement of chemical demand of soluble oxygen by amperometric detection in water quality control applications. As can be seen, the sensor 1 has an external metallic surface 2 that will be destined to be immersed in a water sample 3, this metallic surface 2 comprising a layer of a composite material 4 of multipared and polystyrene carbon nanotubes, said material being 4 also provided with an inorganic catalyst.
    As can be seen, the metal surface 2 is located on a substrate 5, for example an electronic plate, provided with a metal strip 6 that will allow the metal surface 2 and the composite material 4 to be connected with measuring means to control both the potential electrical applied to composite material 4 such as monitoring the electrical current generated in composite material 4.
    Advantageously, the inorganic catalyst of the composite material 4 of the sensor 1 comprises a nano-powder of CuO and AgO, of the order of micrometers, which will favor the oxidation of the organic matter present in the water sample 3 when said composite material 4 is submerged in a water sample 3 whose pH has been adjusted to be greater than 12, when the inorganic catalyst undergoes a chemical reduction reaction, obtaining an electric current as an electrochemical signal by subsequently applying an oxidation activation potential, whereby the Inorganic catalyst is oxidized to its original state. This electric current registered when applying the oxidation potential will be directly proportional to the chemical oxygen demand of the water sample 3 as will be illustrated below, which will allow to determine this parameter of the water sample 3 in which it is found submerged sensor 1.
    The composite material 4 of the sensor 1 comprises 5.9% of CuO and 0.1% of AgO that act as an inorganic catalyst, the rest of the material 4 being 13.4% of multipared carbon nanotubes and 80.6% of polystyrene. As can be seen in Fig. 3, which represents an electronically scanning microscope image of the surface of composite material 4, the inorganic catalyst particles are distributed in said composite material 4.


    Advantageously, this composite material 4 is stable stored at room temperature, so it will not be necessary to store the sensor 1 at a controlled temperature, although it is preferable that it be stored immersed in a solution of pH equal to or greater than 12, thus ensuring that stay conditioned, avoiding possible drifts and loss of sensitivity.
    The metal surface 2 of the sensor 1 will have an area of about 9 mm and preferably will be gold or platinum forming a thin flat sheet on which the layer of composite material 4 will be fixed. This metallic surface 2 can in turn be part of a silicon chip.
    This sensor 1 can be manufactured by following the steps of preparing a suspension of solids comprising carbon nanotubes, polystyrene and an inorganic catalyst in an organic solvent, such as toluene, and depositing the suspension on the metal surface 2 of sensor 1, which will be disposed on a substrate 5 provided with a metal strip 6 or other equivalent electrical connection means. After depositing the suspension on the metal surface 2 of the sensor 1, the solvent must be removed from the suspension by drying at a temperature below 100 degrees Celsius, resulting in a layer of composite material 4 that will be formed and fixed on the metal surface 2.
    Naturally, 6% of the solids in the suspension will be the inorganic catalyst, 5.9% being CuO and 0.1% AgO, preferably in the form of a nano-powder. In addition, the suspension solids will comprise 13.4% of multipared carbon nanotubes and 80.6% of polystyrene that will form the composite material 4 described above.
    In order to perform the detection of chemical oxygen demand in the water sample 3, the sensor 1 must be integrated in an electrochemical cell, in which said sensor 1 will act as a working electrode 11 together with a reference electrode 12, against which the potential to apply the working electrode 11, and an auxiliary electrode 13 will be measured, with which the circuit will be closed allowing the measurement of the current. Said working electrode 11, reference electrode 12 and auxiliary electrode 13 can be integrated into a probe 10 to perform the chemical demand measurement of soluble oxygen based on amperometric detection for water quality control applications as illustrated in Fig. 4, in which the working electrode 11, reference electrode 12 and auxiliary electrode 13 are arranged on the same substrate 5, in this case a printed circuit board 14, and each has a metallic strip 6 on said plate printed circuit 14 to connect each


    electrode in a connector 15 disposed in said printed circuit board 14 that will facilitate the interconnection of the probe 10 with measuring means 16, such as a potentiostat of those known in the state of the art. It is envisioned that these measuring means 16 can either be programmable or can be externally controlled by means of control 29 that allow the chemical oxygen demand measurement sequence to be carried out as will be described later. It is also contemplated that the measuring means 16 are integrated in the control means 29.
    As can be seen in Fig. 4, the probe 10, which is immersed in a sample of water 3 in a cuvette 21, integrates the working electrode 11 which will be a sensor 1 as described above, a reference electrode 12, for example an Ag / AgCl electrode and an auxiliary electrode 13 of known type, thus forming an electrochemical cell. It is envisioned that reference electrodes 12 and auxiliary 13 are covered with a polymeric membrane, for example of Naphion, to keep them clean when they come into contact with sewage. Naturally, the working electrode 11, especially its layer of composite material 4, has to be in contact with the water sample 3 of which it is desired to analyze the chemical oxygen demand.
    It is also provided that the electrodes 11, 12, 13 are packed in a housing 17, for example methacrylate, forming a compact assembly that can be easily manipulated by an operator, allowing the probe 10 to be easily removed for cleaning or replacement. . It is also provided in other embodiments: that reference and auxiliary electrodes 13 are not integrated in the probe 10, but are external to it.
    To perform the chemical demand measurement operation of soluble oxygen based on amperometric detection for water quality control applications in a water sample 3 by means of a probe 10 such as that of Fig 4, which is provided with a working electrode 11 which is the sensor 1 described above, a reference electrode 12 and an auxiliary electrode 13, the working electrodes 11, reference 12 and auxiliary 13 must be immersed in the water sample 3 of which you want to measure the chemical oxygen demand. As illustrated in Fig. 4, the probe 10 is inclined and inserted into a cuvette 21, so that the electrodes 11, 12 and 13 are in contact with the water sample 3.
    Initially, a basic solution should be added to the water sample until the pH of the water sample 3 reaches a pH of 12, since the inorganic catalyst is only


    effective for a pH greater than 12. Naturally this step will not be necessary if the water sample already has a pH equal to or greater than 12.
    When the pH of the water sample 3 is achieved to be equal to or greater than 12, starting from a potential of 0V between the working electrode 11 and the reference electrode 12, an activation potential of between +0.4 and +0.7 V between the working and reference electrodes 11, and detecting the faradaic current generated between the working electrode 11 and the auxiliary electrode 13 when the activation potential is applied, so that the values of this can finally be analyzed electric current by applying an algorithm corresponding to a model previously obtained by PLS analysis to detect the chemical oxygen demand of the water sample 3. Naturally, it is also provided in other variants of embodiment that a pulse train of between 0V can be applied and said activation potential and detecting a sequence of currents to which the corresponding algorithm will be applied to a model previously obtained by PLS analysis using said pulse train.
    As can be seen in the cyclic voltamperogram shown in Fig. 5, although differentiated faradaic currents are obtained for different levels of chemical oxygen demand in the range of voltages of + 0.4V and + 0.7V, the faradaic currents are more proportional and differentiated when the voltage is + 0.6V, so this voltage will be preferred for the detection of chemical oxygen demand in the water sample 3. The graphs shown in Figs. 5 and 6 are based on laboratory tests, in which solutions with different glucose concentrations have been used, since 200uL of glucose equals 261 ppm of O2.
    It is observed that in the range of voltages between 0.4V and 0.7V it is possible to generate a differentiated current for each solution of soluble oxygen, and it has been observed that when the voltage is 0.6V the currents generated for different concentrations is directly proportional to the chemical demand of oxygen in the water, therefore this activation voltage will be the most adequate to measure the chemical demand of oxygen in a water sample 3 by means of the probe 1 of the present invention, although approximate results could also be achieved with an activation potential between 0.4V and 0.7V, but expecting a greater margin of error. Therefore, this sensor 1 will have an interval in which its response is linear with the concentration, between 0 and 1000 mg / L of O2, with the estimated detection limit following the IUPAC criteria of 28 mg / L of O2 with a time answer


    less than 1 min.
    Therefore, the electrical current recorded after applying an activation potential of + 0.6V to the working electrode 11, for example for 60 seconds, will be established as an analytical signal and response of sensor 1, thus obtaining the chronoamperometric response of sensor 1 for different glucose concentrations shown in Fig. 6, from which the calibration curve shown in Fig. 7 can be drawn up, which will allow to determine the chemical oxygen demand in a sample using sensor 1, preferably integrated in a probe 10, of the present invention, by means of an algorithm corresponding to a model previously obtained by PLS analysis that will allow to detect the chemical oxygen demand of a water sample.
    To perform periodic measurements of the chemical oxygen demand automatically using the sensor 1 of the present invention, for example to monitor the chemical oxygen demand in a river, reservoir, etc. The probe 10 provided with the sensor 1 can be integrated into a device 20 as shown in Fig. 8.
    The equipment 20 schematically illustrated in Fig. 8 allows to automatically measure the chemical demand of soluble oxygen based on amperometric detection for water quality control applications using the probe 10 described above. The equipment 20 comprises a cuvette 21 to accommodate a water sample 3; a probe 10 with a working electrode 11 which is the sensor 1 described above; a reference electrode 12 and an auxiliary electrode 13, preferably integrated in the same probe 10; means for adding a base solution 22 to the cuvette 21, to add means for adding a standard solution 23 to the cuvette, means for adding a cleaning solution 24 to the cuvette, recirculating means 25 for the water sample in the bucket, filling means 26 of a water sample in the bucket; and drainage means 27 of the cuvette, and pH measuring means 28 of the water sample 3 contained in the cuvette 21 being the working electrode 11, the reference electrode 12 and auxiliary electrode 13 adapted to be submerged in the sample of water housed in the cuvette and connected to measuring means 16 such as a potentiostat. Naturally, the different components of the equipment 20 will be controlled by programmable control means 29, such as a computer, to control the sequence of events of the equipment 20 in addition to recording the different readings of the chemical oxygen demand to elaborate for example a register historical or able to alert if the chemical oxygen demand


    exceeds a predetermined alert threshold.
    Therefore, by means of the equipment 20 of Fig. 8, the chemical demand measurement of soluble oxygen based on amperometric detection can be performed for water quality control applications by automatically performing the steps controlled by the control means 29 programmable of filling the cuvette 21 with a water sample 3 of the water source to be analyzed; add a basic solution through means of adding a base solution 22 to the cuvette, until the pH of the water sample contained in the cuvette reaches a pH of 12 or higher, so that the sensor 1 of the probe 10 can be used to measure the COD of water sample 3 as specified above. To homogenize the distribution of dissolved or suspended elements in the water sample 3, it is preferable to recirculate the water sample in the cuvette 21 while applying an activation potential between +0.4 and +0.7 V, preferably + 0.6V, between the working electrode 11 and the reference electrode 12 that will be submerged in the water sample 3 of the cuvette
    21. In this way it will be possible to detect the faradaic current generated in the working electrode 11 by applying said activation potential between the working electrode 11 and the reference electrode 12. By detecting the temporal sequence of the values of said current Faradaic and applying an algorithm corresponding to a model previously obtained by PLS analysis, it is possible to measure the chemical demand of soluble oxygen in the water sample 3. Naturally, it is also contemplated to apply pulse trains with the activation potential, that is, between the sensor and the reference electrode submerged in water and measure the pharaic current recorded in the sensor for each pulse and apply an algorithm corresponding to a model previously obtained by PLS analysis.
    It is further envisaged that the equipment 20 comprises a previous calibration stage comprising the phases of filling the cuvette 21 with a standard base solution, for example a standard glucose solution known prepared in a 0.1M NaOH solution. This 0.1M NaOH medium will already set a pH above 12 that will be necessary for the correct operation of the sensor 1, as previously indicated, and while this standard base solution contained in the cuvette 21 is recirculated, apply the potential of activation between the working electrode 11 and the reference electrode 12 in order to detect the faradaic current recorded in the sensor 1 when applying this potential; and perform a PLS analysis to determine, based on the expected response from the known standard base solution, a model based on the results obtained, thus setting the weighting coefficients of the PLS model to calibrate the measurement means for the following measurements.


    It is also provided that the equipment 20 allows a cleaning sequence to be carried out between successive COD measurements of different water samples 3, by injecting a cleaning solution and air by means of adding cleaning solution 24 into the cuvette 21, and recirculating this cleaning solution in the bowl 21 by operating the recirculation means 25, to
    5 finally emptying the cleaning solution of the cuvette 21 by means of the emptying means 27 of the cuvette 21. This will prevent contamination between successive water samples 3 to be analyzed.
    Additionally, to prevent the probe 10 from losing sensitivity between analyzes, it will be configured
    10 the equipment 20 so that at rest the probe 10 is submerged in a conditioning solution of pH 12, which will be incorporated into the cuvette 21 by means of adding maintenance solution 30, thus ensuring that the sensor 1 of the probe 10 is always conditioned between measurements, avoiding possible drifts and loss of sensitivity.

    权利要求:
    Claims (13)
    [1]
    1. Sensor (1) for measuring chemical demand for soluble oxygen based on amperometric detection for water quality control applications, which has
    5 an external metal surface (2) intended to be submerged in a sample ofwater (3) comprising a layer of a nanotube composite material (4) ofmultipared carbon and polystyrene, characterized in that the composite material layerIt also comprises an inorganic catalyst.
    Sensor 2. (1) according to the preceding claim, characterized in that the material (4) comprises 6% inorganic catalyst
    [3]
    3. Sensor (1) according to the preceding claim, characterized in that the catalyst
    Inorganic comprises a nano-powder of CuO and AgO. fifteen
    [4]
    4. Sensor (1) according to any one of the preceding claims, characterized in that the material (4) comprises, as an inorganic catalyst:
    - 5.9% of CuO 20 - 0.1% of AgO
    [5]
    5. Sensor (1) according to any one of the preceding claims, characterized in that the material (4) comprises:
    25 - 13.4% of multipared carbon nanotubes - 80.6% polystyrene
    [6]
    6. Sensor (1) according to any one of the preceding claims, characterized by
    that the metal surface (2) is flat and has an area of 9 mm2. 30
    [7]
    7. Use of a sensor (1) according to any one of the preceding claims for the measurement of chemical demand of soluble oxygen by amperometric detection in water quality control applications.
    35 8. Method of manufacturing a sensor (1) for the chemical demand measurement of
    soluble oxygen based on amperometric detection for control applications of -14

    water quality comprising the steps of:
    - prepare a suspension of solids comprising carbon nanotubes,polystyrene and an inorganic catalyst in an organic solvent;5 - deposit the suspension on a metal surface (2) of an electrode; Y
    - Remove the solvent from the suspension by drying at a temperature below 100 degrees Celsius, forming a layer of composite material (4) on the metal surface.
    Method of manufacturing a sensor (1) according to the preceding claim, characterized in that 6% of the solids in the suspension are an inorganic catalyst.
    [10]
    10. Method of manufacturing a sensor (1) according to any one of the
    The preceding claims, characterized in that the inorganic catalyst of the solids of the suspension comprises a nano-powder of CuO and AgO.
    [11]
    11. Method of manufacturing a sensor (1) according to any one of the
    previous claims, characterized in that the solids of the suspension 20 comprise:
    - 5.9% of CuO
    - 0.1% AgO
    Method of manufacturing a sensor (1) according to any one of the preceding claims, characterized in that the solids of the suspension comprise:
    - 13.4% multipared carbon nanotubes 30 - 80.6% polystyrene
    [13]
    13. Probe (10) for the measurement of chemical demand for soluble oxygen based on amperometric detection for water quality control applications comprising a working electrode (11) formed by a sensor (1) according to a
    Any one of claims 1 to 5.

    [14]
    14. Probe (10) according to the preceding claim, characterized in that it further comprises a reference electrode (12) and an auxiliary electrode (13).
    [15]
    fifteen. Probe (10) according to the preceding claim, characterized in that the electrode
    5 work (11), the reference electrode (12) and the auxiliary electrode (13) areencapsulated in a printed circuit board (14) provided with a connector (15) forits connection with measuring means (16).
    [16]
    16. Procedure for measuring chemical demand for soluble oxygen based on
    10 amperometric detection for water quality control applications in a water sample (3) by means of a probe (10) according to any one of claims 13 to 15 provided with a working electrode (11) which is an electrode
    (1) according to any one of claims 1 to 6; a reference electrode (12)
    and an auxiliary electrode (13), the working, reference and auxiliary electrodes 15 being immersed in the water sample, comprising the steps of:
    - add a basic solution to the water sample until the pH of the water sample reaches a pH of 12; - apply an activation potential between +0.4 and +0.7 V between the working electrode and the reference electrode; - detect the faradaic current generated in the working electrode when applying the activation potential and - apply an algorithm corresponding to a model previously obtained by PLS analysis to detect the chemical oxygen demand of the water sample.
    [17]
    17. Method according to the preceding claim, characterized in that the activation potential is + 0.6V.
    30 18. Equipment (20) for measuring chemical demand of soluble oxygen based on amperometric detection for water quality control applications comprising:
    - a cuvette (21), to accommodate a water sample (3), 35 - a probe (10) according to any one of claims 13 to 15 with a working electrode (11) which is an electrode according to any one of the

    claims 1 to 6; - a reference electrode (12); - an auxiliary electrode (13); - means for adding a base solution (22) to the cuvette,
    5 - means for adding a standard solution (23) to the cuvette,- means for adding a cleaning solution (24) to the cuvette,- recirculation means (25) of the water sample in the bucket,- filling means (26) of a sample of water in the bucket; Y- means for emptying (27) of the bucket,
    10 the working electrode, the reference electrode and auxiliary electrode adapted to be immersed in the sample of water housed in the cuvette and connected to measuring means (16).

    DRAWINGS
     Fig. 2 
     Fig. 3 

    fifteen

    1412108
     Fig. 7
    64
    y = 0.0068 (0.0004) x + 4.0 (0.2) R2
    0 0 200 400 600 800 1000 1200 1400
    COD / mg L-1 O
    Current / µA

    22 23
    24
    26
    Fig. 8
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    同族专利:
    公开号 | 公开日
    ES2595114B1|2017-10-09|
    引用文献:
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    WO2004025672A2|2002-09-11|2004-03-25|Korea Biosystems Corp.|Composite electrode for electrochemical cod measurement|CN107291113A|2017-07-04|2017-10-24|中国科学院国家空间科学中心|A kind of vacuum temperature control light path purifier|
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