US20200124566A1 - Systems and methods for detecting and measuring oxidizing compounds in test fluids - Google Patents
Systems and methods for detecting and measuring oxidizing compounds in test fluids Download PDFInfo
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- US20200124566A1 US20200124566A1 US16/167,295 US201816167295A US2020124566A1 US 20200124566 A1 US20200124566 A1 US 20200124566A1 US 201816167295 A US201816167295 A US 201816167295A US 2020124566 A1 US2020124566 A1 US 2020124566A1
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Images
Classifications
-
- 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
- G01N33/18—Water
- G01N33/182—Specific anions in water
-
- 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
- G01N27/416—Systems
- G01N27/4166—Systems measuring a particular property of an electrolyte
-
- 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
- G01N27/416—Systems
- G01N27/4166—Systems measuring a particular property of an electrolyte
- G01N27/4167—Systems measuring a particular property of an electrolyte pH
-
- 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
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/38—Cleaning of electrodes
-
- 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
- G01N27/416—Systems
- G01N27/4161—Systems measuring the voltage and using a constant current supply, e.g. chronopotentiometry
-
- 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
- G01N27/416—Systems
- G01N27/4166—Systems measuring a particular property of an electrolyte
- G01N27/4168—Oxidation-reduction potential, e.g. for chlorination of water
Definitions
- This disclosure is related to systems, methods, apparatuses, and techniques for detecting and measuring compounds in test fluids.
- Oxidizing compounds can be used to sanitize drinking water. In doing so, it is important to effectively measure the concentration of the oxidizing compounds to ensure both that a sufficient amount of the oxidizing compounds can be applied to sterilize the water, and that the water is safe for consumption.
- FIG. 1 is a block diagram of a system in accordance with certain embodiments
- FIG. 2 is a circuit diagram of a control board that may be utilized by a measurement device in accordance with certain embodiments
- FIG. 3 is a diagram illustrating how measurements are computed in accordance with certain embodiments
- FIG. 4 is a flow chart of an exemplary method in accordance with certain embodiments.
- FIG. 5 is a flow chart of a second exemplary method in accordance with certain embodiments.
- FIG. 6 is a flow chart of a third exemplary method in accordance with certain embodiments.
- a system comprises an improved measurement device that includes reference electrodes constructed of noble metals, passivated transition metals, and/or glassy carbons to prevent, or at least mitigate, oxidation of the reference electrodes, thus extending the lifetime of the measurement device and increasing the reliability of any measurements taken using the measurement device.
- the improved measurement device utilizes electrolysis to detect and measure oxidizing compounds in the test fluids. The measurement device can be utilized to make a variety of different measurements.
- the measurement device can use water electrolysis to measure oxidizing compounds (e.g., ozone) in water, such as drinking water and/or other types of water, using oxidation reduction potential (ORP) measurement techniques.
- oxidizing compounds e.g., ozone
- ORP oxidation reduction potential
- the probe can use electrolysis to take pH measurements, ion concentration measurements, potentiometric measurements, and/or other measurements.
- a system comprises: (i) a test fluid comprising a concentration of an oxidizing compound; and (ii) a measurement device configured to: apply a constant current to the test fluid; measure a reference voltage indicating an electrochemical potential at which electrolysis occurs in the test fluid; measure a second voltage indicating an oxidizing potential of the test fluid; and calculate an oxidizer concentration measurement indicating the concentration of the oxidizing compound in the test fluid based on a voltage difference between the reference voltage and the second voltage.
- a method comprises: applying a constant current to a test fluid comprising a concentration of an oxidizing compound; measuring, with a measurement device, a reference voltage indicating an electrochemical potential at which electrolysis occurs in the test fluid; measuring, with the measurement device, a second voltage indicating an oxidizing potential of the test fluid; and calculating, with the measurement device, an oxidizer concentration measurement indicating the concentration of the oxidizing compound in the test fluid based on a voltage difference between the reference voltage and the second voltage.
- a system comprises: (i) a test fluid comprising a concentration of an oxidizing compound; and (ii) a measurement device comprising: (a) a processor; (b) a power supply that is configured to provide a constant current; and (c) a first electrode, a second electrode, and a third electrode, wherein: the first electrode and the second electrode are included on a circuit to which the constant current is applied when the first electrode and the second electrode are submerged in the test fluid, and the third electrode is not included on the circuit; the first electrode, the second electrode, and the third electrode are each comprised of a noble metal, a passivated transition metal, a glass-like carbon, or some combination thereof; the first electrode is configured to measure a reference voltage indicating an electrochemical potential at which electrolysis occurs in the test fluid; the third electrode is configured to measure a second voltage indicating an oxidizing potential of the test fluid; and the measurement device calculates an oxidizer concentration measurement indicating the concentration of the oxidizing compound in the test
- a system comprising: a test fluid; and a measurement device configured to: apply a constant current to the test fluid; measure a reference voltage indicating an electrochemical potential at which electrolysis occurs in the test fluid; measure a second voltage indicating a potential of the test fluid related to one of an oxidizing potential, a pH potential, or an ion concentration chemical potential; and calculate a concentration measurement in the test fluid based on a voltage difference between the reference voltage and the second voltage.
- any aspect or feature that is described for one embodiment can be incorporated into any other embodiment mentioned in this disclosure.
- any of the embodiments described herein may be hardware-based, may be software-based, or, preferably, may comprise a mixture of both hardware and software elements.
- the description herein may describe certain embodiments, features, or components as being implemented in software or hardware, it should be recognized that any embodiment, feature, or component that is described in the present application may be implemented in hardware and/or software.
- FIG. 1 is a block diagram of a system 100 in accordance with certain embodiments.
- the system 100 includes a measurement device 150 , which includes electrodes 140 and a temperature measurement component 170 that are immersed in a test fluid 160 .
- the test fluid 160 can be a liquid or a gas.
- the system 100 further includes a computing device(s) 110 , a water management system 180 , and an oxidizer generator 120 .
- the computing device 110 , the measurement device 150 , the water management system 180 , and the oxidizer generator 120 can be in indirect communication with each other over a network 130 and/or in direct communication with each other.
- the network 130 may represent any type of communication network, e.g., such as one that comprises a local area network (e.g., a Wi-Fi network), a personal area network (e.g., a Bluetooth network), a wide area network, an intranet, the Internet, a cellular network, and/or other types of networks.
- a local area network e.g., a Wi-Fi network
- a personal area network e.g., a Bluetooth network
- a wide area network e.g., an intranet, the Internet, a cellular network, and/or other types of networks.
- computing device 110 may depict a single one of each of computing device 110 , measurement device 150 , water management system 180 , and oxidizer generator 120 , it should be understood this is not intended to be limiting, and the system can include any number of each component (e.g., computing devices 110 , measurement devices 150 , water management systems 180 , and oxidizer generators 120 ) and sub-component (e.g., electrodes 140 and multiple temperature measurement components 170 ), and all of the components and sub-components can be configured to communicate with each other directly or indirectly.
- each component e.g., computing devices 110 , measurement devices 150 , water management systems 180 , and oxidizer generators 120
- sub-component e.g., electrodes 140 and multiple temperature measurement components 170
- All the components illustrated in FIG. 1 including the computing device 110 , the measurement device 150 , the water management system 180 , and the oxidizer generator 120 can be configured to communicate directly with each other and/or over the network 130 via wired or wireless communication links, or a combination of the two.
- Each of the computing device 110 , the measurement device 150 , the water management system 180 , and the oxidizer generator 120 can include one or more communication devices.
- the communication devices can include any device for communicating over a wired and/or wireless communication channel or communication link.
- communication devices can include one or more of the following: transceivers, transmitters, receivers, communication cards, network connectors, network adapters, and/or integrated circuits. Other types of communication devices also can be used.
- the computing devices 110 may represent desktop computers, laptop computers, mobile devices (e.g., smart phones, personal digital assistants, tablet devices, or any other devices that are mobile in nature), and/or other types of computing devices.
- Each of the computing device 110 , the measurement device 150 , the water management system 180 , and the oxidizer generator 120 also can be equipped with one or more computer storage devices and one or more processing devices that are capable of executing computer program instructions.
- the computer storage devices may be physical, non-transitory mediums in certain embodiments.
- the one or more storage devices can communicate with the one or more processors, and the one or more processors can execute any instructions stored on the one or more storage devices.
- the one or more storage devices may include: i) non-volatile memory, such as, for example, read only memory (ROM) or programmable read only memory (PROM); and/or (ii) volatile memory, such as, for example, random access memory (RAM), dynamic RAM (DRAM), static RAM (SRAM), etc.
- RAM random access memory
- DRAM dynamic RAM
- SRAM static RAM
- the one or more storage devices can comprise (i) non-transitory memory and/or (ii) transitory memory.
- the one or more processors can include one or more central processing units (CPUs), controllers, microprocessors, digital signal processors, and/or computational circuits.
- Embodiments or aspects of the techniques described herein may include a computer program product accessible from a computer-usable or computer-readable medium providing program code for use by or in connection with a computer or any instruction execution system.
- a computer-usable or computer-readable medium may include any apparatus that stores, communicates, propagates, or transports the program for use by or in connection with the instruction execution system, apparatus, or device.
- the medium can be a magnetic, optical, electronic, electromagnetic, infrared, or semiconductor system (or apparatus or device) or a propagation medium.
- the medium may include a computer-readable storage medium, such as a semiconductor or a solid state memory, a magnetic tape, a removable computer diskette, a random access memory (RAM), a read-only memory (ROM), a rigid magnetic disk, and an optical disk.
- a computer-readable storage medium such as a semiconductor or a solid state memory, a magnetic tape, a removable computer diskette, a random access memory (RAM), a read-only memory (ROM), a rigid magnetic disk, and an optical disk.
- the measurement device 150 can be utilized to make a variety of different measurements.
- the measurement device 150 can use water electrolysis to measure oxidizing compounds 165 in water, such as drinking water and/or other types of water, using oxidation reduction potential (ORP) measurement techniques.
- the measurement device 150 can use electrolysis to take pH measurements, ion concentration measurements, potentiometric measurements, and/or other measurements.
- the measurement device 150 includes at least three electrodes 140 .
- Each of the electrodes 140 can be constructed of a noble metal, a passivated transition metal, or a glass-like carbon (also referred to as “glassy carbons” or “vitreous carbons”).
- the electrodes are constructed of gold, platinum, titanium, or a glass-like carbon, or of some combination thereof.
- the electrodes can additionally, or alternatively, be constructed of other similar metals, compounds, or other materials that do not oxidize under the conditions applied to the measurement device 150 when the measurement device is submerged in the test fluid 160 . Using such construction materials avoids the risk of corrosion, which can reduce the lifetime of the measurement device 150 , elute ions into the test fluid, and cause the measurement device 150 to be insensitive to the oxidizing compounds 165 being measured.
- Two of the electrodes 140 can be configured on a circuit as a reference pair, and a third one of the electrodes 140 can be used as a sensor electrode.
- the sensor electrode may not be included on the circuit with the reference pair.
- electrolysis will split the molecules of the test fluid 160 , and the electrochemical potential at which electrolysis occurs can be used as a reference voltage.
- the test fluid 160 is water
- the reference pair electrolyzes the water to split the molecules into hydrogen and oxygen.
- the reference electrodes can conduct water oxidation and/or water reduction and, therefore, evolve oxygen gas or hydrogen gas.
- the constant current that is applied is 10 microamperes (uA).
- the electrode 140 that is used as sensor electrode can be connected to one of the electrodes 140 included in the reference pair using a high impedance resistor, an operational amplifier, and/or another component. By measuring the voltage across this connection, the voltage difference between the reference electrodes and the sensor electrode can be calculated. As oxidizing compounds 165 are added to the test fluid 160 (e.g., to sanitize the test fluid 160 ), the potential on the sensor electrode will increase, and the measured voltage between the reference pair and the sensor electrode will change. Because this change is relative to the concentration of the oxidizing compounds 165 , the voltage measurement can be calibrated as an oxidizer concentration measurement (e.g., V ac in FIG. 2 ) that indicates the amount of oxidizing compounds 165 in the test fluid 160 .
- an oxidizer concentration measurement e.g., V ac in FIG. 2
- one of the electrodes 140 included in the reference pair can measure a voltage indicating an electrochemical potential at which electrolysis occurs in the test liquid 160
- the sensor electrode can measure a voltage indicating an oxidizing potential of the test fluid 160 .
- the measurement device 150 can then subtract the voltage measured by the sensor electrode from the voltage measured by the electrode 140 included in the reference pair to calculate the oxidizer concentration measurement.
- the measurement device 150 also can be configured to execute a self-cleaning function on the electrodes 140 .
- a self-cleaning function During normal operation (e.g., when the measurement device 150 is operating in a potentiometric mode and is being utilized to measure and/or control levels of oxidizing compounds 165 in the test fluid 160 ), the surface of the electrodes 140 may be reduced, thereby causing a gain in electrons.
- the measurement device 150 also can be operated in a reverse polarization mode that executes the self-cleaning function.
- the measurement device 150 utilizes an H-bridge, or other equivalent electrical component, to reverse the current that is applied to the reference pair of electrodes 140 . This reversal of the current can produce a redox (or reduction-oxidation) reaction on the reference pair of electrodes 140 , which is inverse to that current used during normal operation and which reverses the reduction by oxidizing the surface of the electrodes 140 .
- the measurement device 150 also can take measurements of the oxidizing compounds 165 when operating in the chronopotentiometric mode.
- the measurements taken by the measurement device 150 in the chronopotentiometric mode can be used to confirm the accuracy of the measurements taken by the measurement device 150 in the normal or potentiometric mode.
- the measurement device 150 can short one or more of the electrodes 140 to an electrical ground, which can have the effect of applying a reducing potential to electrodes 140 and purging the surface of the electrode of oxidizing compounds 165 by a process of electrochemical reduction.
- the concentration of the oxidizing compounds 165 may be deduced by measuring both the maximum voltage and the time to reach that maximum voltage. As the recovery time will be shortened with increases in concentration of oxidizing compounds 165 , a chronopotentiometric measurement of oxidizer concentration can be ascertained.
- the measurement device 150 can include a fourth electrode 140 , which also is constructed of a noble metal, a passivated transition metal, a glass-like carbon, and/or some combination thereof.
- This fourth electrode 140 can be paired with the sensor electrode, thus allowing either pair of electrodes to be used as a reference pair in taking measurements and/or to implement the self-cleaning procedure. It should be noted that the fourth electrode 140 is optional, and the measurement device 150 is capable of functioning without the inclusion of the fourth electrode 140 .
- the measurement device 150 can include a temperature measurement component 170 that is configured to measure or determine the temperature of the test fluid 160 .
- the temperature measurement component 170 can include a thermistor and/or other device that is capable of measuring the temperature of the test fluid 160 .
- the temperature readings generated by the temperature measurement component 170 can be used by the measurement device 150 , along with other data (e.g., oxidizer concentration measurements) to adjust and/or control (e.g., to increase or decrease) the concentration of the oxidizing compounds 165 in the test fluid 160 .
- the measurement device 150 can be used to detect and/or measure oxidizing compounds 165 in various test fluids 160 .
- the tests liquids 160 can include water, (e.g., drinking water, non-potable water, distilled water, deionized water, and/or other types of water).
- the tests liquids 160 can additionally, or alternatively, include alcohols (e.g., ethanol, methanol, and other alcohols) and/or electrolyze-able organic solvents (e.g., acetic acid).
- the measurement device 150 can be used to detect and measure microbial life in test fluids 160 (e.g., water). For example, as aerobic microbial life consumes oxygen in order to live and propagate, a concentration of microbes in a test fluid 160 can reduce the oxidizing compounds 165 . This reduction of oxidizing compounds 165 in the test fluid 160 can therefore be used to measure the microbial life content.
- test fluids 160 e.g., water
- the measurement device 150 can be used to detect and measure various types of oxidizing compounds 165 .
- oxidizing compounds 165 can include, but are not limited to, any or all of the following: oxygen (O2), ozone (O3), hydrogen peroxide (H2O2) (as well as other inorganic peroxides), fluorine (F2), chlorine (Cl2), halogen compounds, nitric acid (HNO3), nitrate compounds, sulfuric acid (H2SO4), peroxydisulfuric acid (H2S2O8), peroxymonosulfuric acid (H2SO5), chlorite, chlorate, perchlorate, hypochlorite (and other hypohalite compounds), household bleach (NaClO), hexavalent chromium compounds (e.g., chromic and dichromic acids and chromium trioxide, pyridinium chlorochromate, and chromate/dichromate compounds), permanganate compounds (e.g.,
- the measurement device 150 also can be used to detect and measure various types of reducing compounds.
- reducing compounds can include, but are not limited to, any or all of the following: hydrogen, diborane, sodium borohydride (NaBH4), sulfur dioxide, sulfite compounds, dithionates (e.g., Na2S2O6), thiosulfates (e.g., Na2S2O3), iodides (e.g., KI), hydrazine, diisobutylaluminium hydride (DIBAL-H), oxalic acid, formic acid (HCOOH), ascorbic acid (C6H8O6), reducing sugars, phosphites, hypophosphites, phosphorous acid, dithiothreitol (DTT), carbon monoxide (CO), cyanides, carbon (C), tris-2-carboxyethylphosphine hydrochloride (TCEP), compounds containing the Fe2
- the measurement device 150 can be incorporated into a water management system 180 .
- the water management system 180 can include any system, device, and/or apparatus that produces, generates, stores, manages, and/or distributes drinking water and/or other types of water.
- the measurement device 150 can be incorporated into a water management system 180 that produces or generates liquid water by extracting water vapor from ambient air or atmospheric air.
- the measurement device 150 and/or related techniques described herein can be utilized in connection with the systems, methods, and apparatuses described in: (i) U.S. patent application Ser. No. 15/482,104 filed on Apr. 7, 2017 (U.S. Patent Publication No.
- the test fluid 160 can be water and the oxidizing compounds 165 (e.g., ozone) can be applied to water in order to sanitize the water and make it safe for consumption.
- the measurement device 150 described herein can be configured to measure the concentration of the oxidizing compounds 165 in the water to ensure that a sufficient amount of the oxidizing compounds 165 has been applied to sterilize the water and/or to ensure that the water is safe for drinking.
- the oxidizer generator 120 can be any device or apparatus that is configured to generate and/or apply oxidizing compounds 165 to the test fluid 160 .
- the oxidizer generator 120 can include an ozone generator that is configured to generate and apply ozone to sterilize water or other test fluids.
- the oxidizer generator 120 can additionally, or alternatively, be configured to generate and/or apply other types of oxidizing compounds 165 to the test fluid, including any of the oxidizing compounds 165 mentioned in this disclosure.
- the measurements taken by the measurement device 150 can be used to control (e.g., to increase or decrease) the concentration of the oxidizing compounds 165 in the test fluid 160 .
- the oxidizer generator 120 may be integrated with the water management system 180 to control the concentration of the oxidizing compounds 165 in test fluids 160 that include water.
- the measurement device 150 can be used in testing liquids 160 other than water and can take a variety of different measurements.
- the electrodes 140 included in the measurement device 150 can include one or more pH electrodes and/or proton selective electrodes that enable the measurement device 150 to apply electrolysis to the test fluid 160 for taking pH measurements, acid concentration measurements, base measurements, and/or the like.
- the electrodes 140 of the measurement device 150 can include one or more ion selective electrodes (ISE) that enable the measurement device 150 to apply electrolysis to the test fluid 160 for taking ion concentration measurements.
- ISE ion selective electrodes
- the measurement device 150 and/or water management system 180 implements a control function for regulating the concentration of the oxidizing compounds 165 in the test fluid 160 .
- the measurement device 150 and/or water management system 180 may regulate the concentration of ozone that is applied to disinfect or sterilize water to ensure that the water is potable and safe for consumption.
- the control function may be implemented using one or more processors (e.g., one or more microcontrollers) integrated into the measurement device 150 and/or water management system 180 .
- the control function can activate the oxidizer generator 120 if the voltage indicating the oxidizer or ozone concentration measurement reaches a first specified threshold (e.g., indicating that ozone should be applied to reduce the concentration of microbial life in the water), and can deactivate the oxidizer generator 120 if the voltage indicating the oxidizer or ozone concentration measurement reaches a second specified threshold (e.g., indicating the current concentration of ozone is sufficient and/or that the water is safe for consumption).
- a first specified threshold e.g., indicating that ozone should be applied to reduce the concentration of microbial life in the water
- a second specified threshold e.g., indicating the current concentration of ozone is sufficient and/or that the water is safe for consumption
- the control function in response to reaching the second threshold, implements a timeout (e.g., 5 minutes, 10 minutes, 15 minutes, or 1 hour) during which the measurement device 150 does not take measurements and the oxidizer generator 120 does not apply oxidizing compounds 165 .
- the control function can be configured to execute a closed loop control technique, in which the measurement device 150 will cause the oxidizer generator 120 to apply ozone to maintain a predefined ozone voltage measurement, and will cut off power to the measurement device 150 and/or oxidizer generator 120 when the voltage is registered as sufficient (e.g., when the voltage reaches the second threshold).
- the computing device 110 can be configured to access the measurement device 150 , the oxidizer generator 120 , and/or the water management system 180 to monitor and/or control various aspects of the system 100 .
- the computing device 110 can be configured to review measurements and other data generated by the measurement device 150 .
- the computing device 110 also can be configured to transmit commands to the measurement device 150 , the oxidizer generator 120 , and/or the water management system 180 for switching between potentiometric and chronopotentiometric modes, executing the self-cleaning function, managing the control functions, adjusting concentrations of oxidizing compounds 165 in the test fluid 160 , and/or performing other related functions.
- the computing device 110 can be operated by an administrator or other individual who is associated with managing the measurement device 150 and/or water management system 180 .
- the embodiments described herein provide a variety of advantages over conventional measurement devices and probes. Some of the advantages include the ability to extend the lifetime of the measurement device 150 and to increase the reliability of any measurements taken using the measurement device 150 . This can be attributed, at least in part, to the structure of the measurement device 150 , which utilizes noble metals, passivated transition metals, and/or glassy carbons for the electrodes 140 immersed in the test fluid 160 , and the electrolysis-based techniques utilized to take the measurements. Another significant advantage is the ability of the measurement device 150 to operate in a reverse polarization mode that allows the measurement device 150 to self-clean the surfaces of the electrodes 140 . A further advantage of the device is the ability to operate in a chronopotentiometric mode to take measurements that can be used to confirm the measurements taken during normal operation. This technology-based solution marks an improvement over existing measurement devices and probes.
- FIG. 2 is a circuit diagram of a control board 200 that may be utilized by a measurement device (e.g., measurement device 150 in FIG. 1 ) in accordance with certain embodiments.
- the control board 200 may be utilized for a measurement device that is assessing water and applying ozone as an oxidizing compound to sterilize the water.
- the control board 200 includes, inter alia, the following components: a microcontroller 210 , a power supply 220 , an H-bridge 230 , a MOSFET (metal-oxide-semiconductor field-effect transistor) 240 , a pair of resistors 250 , and an operational amplifier (op amp) 260 .
- the power supply 220 can be a 10 uA constant current supply
- the MOSFET 240 can be an N-channel MOSFET
- the op amp 260 can be a differential op amp
- the resistors 250 can be 30 megaohms (Mohms) resistors.
- different types of components can be integrated into the control board 200 based on the test fluid and/or based on the types of measurements that are being deduced.
- the control board 200 also includes three electrical connections—A, B, and C—for each of three connected electrodes (e.g., electrodes 140 in FIG. 1 ).
- the three electrical connections—A, B, and C— may be connected to wires, and the electrodes can be attached to the end of the wires and suspended in the test fluid.
- the electrodes corresponding to electrical connections A and B form the reference pair, and the electrical connection C corresponds to the sensor electrode.
- the measurement device may include a fourth electrode as well.
- an additional electrical connection can be added to the control board 200 to facilitate connection of the fourth electrode.
- the fourth node can be included on a circuit with the electrical connection C corresponding to the sensor electrode.
- T 1 and T 2 are electrical connections to a temperature measurement component (e.g., temperature measurement component 170 in FIG. 1 ).
- the power supply 220 may be configured to regulate a fixed current by adjusting the output voltage as the load changes.
- a constant current power supply provides a regulated 1 or 10 pA of current ranging from 0 to 3 VDC (volts DC).
- the constant current supply may be implemented using an instrumentation operational amplifier. When the current is applied to electrodes A and B, the water or test fluid will be electrolyzed, and this circuit will be used to produce V ab , which is a measure of the test fluid conductivity, and Ref, which is a measure of the electrochemical potential at which electrolysis occurs in the test fluid. Under ideal conditions, water electrolysis occurs at ⁇ 1.23 V (volts).
- Electrode C measures a voltage indicating an oxidizing potential of the test fluid, which is shown as V 0p .
- Ref and V 0p are passed through the resistors 250 and supplied to op amp 260 .
- Op amp 260 subtracts V 0p from Ref to produce V ac , which serves as an indicator of the oxidation potential voltage.
- T 1 is the electrical connection to the temperature measurement component and T 2 is a connection to a ground associated with the temperature measurement component.
- Temp is a voltage indicating the temperature of the test fluid.
- the microcontroller 210 receives the following inputs:
- Temp this is a temperature measurement of the test fluid 160 received from the temperature measurement component (e.g., thermistor);
- SDA/SCL these are I 2 C network signals between the microcontroller 210 and a host controller.
- the outputs of the microcontroller 210 include:
- H-Bridge output signal this output controls the current flow and instructs the H-Bridge whether the current should be reversed (e.g., depending upon whether not the device is operating in the normal mode or the reverse polarization mode);
- MOSFET output signal this output controls whether or not electrode C is connected to a ground by sending instructions to the MOSFET;
- SDA/SCL output signals these outputs are provided as part of an I 2 C network and can communicate the electrode voltage measurements (V ab and V ac ) as well as the temperature measurement (T 1 ) upon request from the host controller.
- the microcontroller 210 can use the electrode voltage measurements (V ab and V ac ) as well as the temperature measurement (T 1 ) to implement the control function for increasing and/or decreasing the concentration of ozone in the water.
- the microcontroller 210 can compare these parameters to a library of pre-stored conditions to activate and/or deactivate an ozone generation system.
- the library may be use the temp measurement, inter alia, to control the current that is applied to the test fluid and/or to control the oxidizing compounds that are applied to the test fluid.
- the measurement device can operate in a potentiometric mode (e.g., during normal operation when the concentration of the ozone or other oxidizing compound is being measured), a chronopotentiometric mode (e.g., during an operation that cleans the sensor electrode and/or takes confirmatory measurements), and a reverse polarity mode (e.g., during a self-cleaning operation that cleans the electrodes and/or takes confirmatory measurements).
- a potentiometric mode e.g., during normal operation when the concentration of the ozone or other oxidizing compound is being measured
- a chronopotentiometric mode e.g., during an operation that cleans the sensor electrode and/or takes confirmatory measurements
- a reverse polarity mode e.g., during a self-cleaning operation that cleans the electrodes and/or takes confirmatory measurements.
- the H-Bridge output signal provided by the microcontroller 210 can instruct the H-Bridge 230 that the current flow is not to be reversed, and the MOSFET output signal can instruct MOSFET 240 that the electrode 140 corresponding to electrical connection C is not to be connected to a ground.
- the H-Bridge output signal provided by the microcontroller 210 can instruct the H-Bridge 230 that the current flow is to be reversed.
- the MOSFET output signal can instruct MOSFET 240 that the electrode corresponding to electrical connection C is to be connected to a ground. Connecting to the ground will close the circuit between electrode C and the ground, and will result in a “purge” that is intended to reduce any residual oxidizer on the surface of the electrode.
- the SDA/SCL connections connect the microcontroller 210 to a host controller.
- the microcontroller 210 acts as a “slave” device and communicates the electrode voltage measurements and temperature measurements upon request from the host controller.
- the microcontroller 210 also can receive commands from the host controller for controlling the H-bridge 230 for electrodes A and B, and the MOSFET 240 (e.g., which may be an N-channel MOSFET) for electrode C.
- FIG. 3 is a diagram 300 illustrating how measurements are computed in accordance with certain embodiments. This diagram illustrates how measurements may be computed by the measurement device (e.g., measurement device 150 in FIG. 1 ) for various embodiments in which ozone concentration is being measured in water.
- the measurement device e.g., measurement device 150 in FIG. 1
- the axis on the left represents a range of possible voltages associated with the electrochemical potential at which the process of water electrolysis occurs. This axis is not labeled because the values may be dependent on the type of electrodes that are used.
- the bracket labeled “Water Electrolysis Voltage 1.23V” represents the voltage to perform water electrolysis under standard conditions.
- Cell voltage represents the measurement of voltage used to conduct water electrolysis, which considers all features of the true voltage measurement (e.g., such as the area of the test fluid 160 and the distance or separation of the electrodes).
- the “Over potentials” for the reference electrodes represent the difference between the cell voltage and the standard water electrolysis voltage.
- the electrochemical reactions for water electrolysis also are listed in the figure.
- An ozone voltage is a function of ozone concentration and can be any value in a range that falls within the water electrolysis reaction voltages. The difference between this voltage and the voltage of the reference is reported as the oxidation potential measurement.
- the reference electrodes are conducting water oxidation and, therefore, are evolving oxygen gas.
- the reference electrodes can additionally, or alternatively, conduct water reduction and, therefore, evolve hydrogen gas.
- FIGS. 4-6 illustrate flow charts for exemplary methods 400 , 500 , 600 , respectively, according to certain embodiments.
- Methods 400 , 500 , 600 are merely exemplary and are not limited to the embodiments presented herein. Methods 400 , 500 , 600 can be employed in many different embodiments or examples not specifically depicted or described herein. In some embodiments, the activities of methods 400 , 500 , 600 can be performed in the order presented. In other embodiments, the activities of methods 400 , 500 , 600 can be performed in any suitable order. In still other embodiments, one or more of the activities of methods 400 , 500 , 600 can be combined or skipped. In many embodiments, system 100 ( FIG. 1 ) and/or measurement device 150 ( FIG.
- one or more of the activities of methods 400 , 500 , 600 can be implemented as one or more computer instructions configured to run at one or more processors and configured to be stored at one or more non-transitory storage devices.
- Such non-transitory memory storage devices can be part of system 100 ( FIG. 1 ), measurement device 150 ( FIG. 1 ) and/or control board 200 ( FIG. 2 ).
- the processor(s) can be similar or identical to the processor(s) described above with respect to system 100 ( FIG. 1 ).
- FIG. 4 is a flow chart of an exemplary method 400 in accordance with certain embodiments.
- Method 400 can comprise an activity 410 of applying a constant current to a test fluid including an oxidizing compound.
- Method 400 can further comprise an activity 420 of measuring a reference voltage indicating an electrochemical potential at which electrolysis occurs in the test fluid.
- Method 400 can further comprise an activity 430 of measuring a second voltage indicating an oxidizing potential of the test fluid.
- Method 400 can further comprise an activity 440 of calculating an oxidizer concentration measurement indicating the concentration of the oxidizing compound in the test fluid based on a voltage difference between the reference voltage and the second voltage.
- system 100 in FIG. 1 and control board 200 in FIG. 2 can be used to perform some or all of one or more of activities 410 , 420 , 430 , and 440 .
- FIG. 5 is a flow chart of a second exemplary method 500 in accordance with certain embodiments.
- Method 500 can comprise an activity 510 of submerging electrodes, including at least a pair of reference electrodes and a sensor electrode in a test fluid that includes oxidizing compounds.
- Method 500 can further comprise an activity 520 of applying a constant current to the pair of reference electrodes submerged in the test fluid.
- Method 500 can further comprise an activity 530 of measuring a conductivity or electrical resistance of the test fluid based on the constant current using the sensor electrode.
- Method 500 can further comprise an activity 540 of measuring an oxidation potential voltage of the test fluid using the pair of reference electrodes.
- Method 500 can further comprise an activity 550 of measuring a temperature of the test fluid using a temperature measurement component.
- Method 500 can further comprise an activity 560 of using the measurements to control an oxidizer generation system that is able to apply oxidizing compounds to the test fluid.
- an oxidizer generation system that is able to apply oxidizing compounds to the test fluid.
- one of or both of system 100 in FIG. 1 and control board 200 in FIG. 2 can be used to perform some or all of one or more of activities 510 , 520 , 530 , and 540 .
- FIG. 6 is a flow chart of a third exemplary method 600 in accordance with certain embodiments.
- Method 600 can comprise an activity 610 of submerging electrodes, including at least a pair of reference electrodes and a sensor electrode in a test fluid that comprises water and ozone.
- Method 600 can further comprise an activity 620 of applying a constant current to the pair of reference electrodes submerged in the test fluid.
- Method 600 can further comprise an activity 630 of measuring, using the sensor electrode, a conductivity or electrical resistance of the test fluid based on the constant current.
- Method 600 can further comprise an activity 640 of measuring, using the pair of reference electrodes, an ozone oxidation potential voltage.
- Method 600 can further comprise an activity 650 of measuring, using a temperature measurement component, a temperature of the test fluid.
- Method 600 can further comprise an activity 660 of utilizing the measurements to control an ozone generation system that is able to apply ozone to the test fluid.
- an activity 660 of utilizing the measurements to control an ozone generation system that is able to apply ozone to the test fluid.
- system 100 in FIG. 1 and control board 200 in FIG. 2 can be used to perform some or all of one or more of activities 610 , 620 , 630 , 640 , 650 , and 660 .
- embodiments and limitations disclosed herein are not dedicated to the public under the doctrine of dedication if the embodiments and/or limitations: (1) are not expressly claimed in the claims; and (2) are, or potentially are, equivalents of express elements and/or limitations in the claims under the doctrine of equivalents.
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Abstract
Description
- This disclosure is related to systems, methods, apparatuses, and techniques for detecting and measuring compounds in test fluids.
- Oxidizing compounds (also referred to “oxidizing agents” or “oxidizers”) can be used to sanitize drinking water. In doing so, it is important to effectively measure the concentration of the oxidizing compounds to ensure both that a sufficient amount of the oxidizing compounds can be applied to sterilize the water, and that the water is safe for consumption.
- Conventional apparatuses for making these measurements are plagued with various deficiencies. One deficiency is that the lifetime and reliability of these apparatuses are limited, thus requiring the measurement apparatuses to be replaced over relatively short periods of time. This deficiency can be attributed, at least in part, to the fact that these apparatuses typically rely on reference electrodes that rapidly lose chloride salts as a result of diffusion processes that take place while the reference electrodes are immersed in test fluids with the oxidizing compounds. This diffusion of salts from the reference electrodes reduces the lifetime of the reference electrodes, affects the reliability of the measurement apparatuses, and often causes failures of the measurement apparatuses.
- To facilitate further description of the embodiments, the following drawings are provided, in which like references are intended to refer to like or corresponding parts, and in which:
-
FIG. 1 is a block diagram of a system in accordance with certain embodiments; -
FIG. 2 is a circuit diagram of a control board that may be utilized by a measurement device in accordance with certain embodiments; -
FIG. 3 is a diagram illustrating how measurements are computed in accordance with certain embodiments; -
FIG. 4 is a flow chart of an exemplary method in accordance with certain embodiments; -
FIG. 5 is a flow chart of a second exemplary method in accordance with certain embodiments; and -
FIG. 6 is a flow chart of a third exemplary method in accordance with certain embodiments. - The present disclosure relates to improved systems, methods, apparatuses, and techniques for detecting and measuring oxidizing compounds in test fluids. In certain embodiments, a system comprises an improved measurement device that includes reference electrodes constructed of noble metals, passivated transition metals, and/or glassy carbons to prevent, or at least mitigate, oxidation of the reference electrodes, thus extending the lifetime of the measurement device and increasing the reliability of any measurements taken using the measurement device. In contrast to conventional measurement devices, the improved measurement device utilizes electrolysis to detect and measure oxidizing compounds in the test fluids. The measurement device can be utilized to make a variety of different measurements. In certain exemplary embodiments, the measurement device can use water electrolysis to measure oxidizing compounds (e.g., ozone) in water, such as drinking water and/or other types of water, using oxidation reduction potential (ORP) measurement techniques. In other exemplary embodiments, the probe can use electrolysis to take pH measurements, ion concentration measurements, potentiometric measurements, and/or other measurements.
- In certain embodiments, a system is provided that comprises: (i) a test fluid comprising a concentration of an oxidizing compound; and (ii) a measurement device configured to: apply a constant current to the test fluid; measure a reference voltage indicating an electrochemical potential at which electrolysis occurs in the test fluid; measure a second voltage indicating an oxidizing potential of the test fluid; and calculate an oxidizer concentration measurement indicating the concentration of the oxidizing compound in the test fluid based on a voltage difference between the reference voltage and the second voltage.
- In certain embodiments, a method is provided that comprises: applying a constant current to a test fluid comprising a concentration of an oxidizing compound; measuring, with a measurement device, a reference voltage indicating an electrochemical potential at which electrolysis occurs in the test fluid; measuring, with the measurement device, a second voltage indicating an oxidizing potential of the test fluid; and calculating, with the measurement device, an oxidizer concentration measurement indicating the concentration of the oxidizing compound in the test fluid based on a voltage difference between the reference voltage and the second voltage.
- In certain embodiments, a system is provided that comprises: (i) a test fluid comprising a concentration of an oxidizing compound; and (ii) a measurement device comprising: (a) a processor; (b) a power supply that is configured to provide a constant current; and (c) a first electrode, a second electrode, and a third electrode, wherein: the first electrode and the second electrode are included on a circuit to which the constant current is applied when the first electrode and the second electrode are submerged in the test fluid, and the third electrode is not included on the circuit; the first electrode, the second electrode, and the third electrode are each comprised of a noble metal, a passivated transition metal, a glass-like carbon, or some combination thereof; the first electrode is configured to measure a reference voltage indicating an electrochemical potential at which electrolysis occurs in the test fluid; the third electrode is configured to measure a second voltage indicating an oxidizing potential of the test fluid; and the measurement device calculates an oxidizer concentration measurement indicating the concentration of the oxidizing compound in the test fluid based on a voltage difference between the reference voltage and the second voltage.
- In certain embodiments, a system is provided that comprises: a test fluid; and a measurement device configured to: apply a constant current to the test fluid; measure a reference voltage indicating an electrochemical potential at which electrolysis occurs in the test fluid; measure a second voltage indicating a potential of the test fluid related to one of an oxidizing potential, a pH potential, or an ion concentration chemical potential; and calculate a concentration measurement in the test fluid based on a voltage difference between the reference voltage and the second voltage.
- The embodiments described in this disclosure can be combined in various ways. Any aspect or feature that is described for one embodiment can be incorporated into any other embodiment mentioned in this disclosure. Moreover, any of the embodiments described herein may be hardware-based, may be software-based, or, preferably, may comprise a mixture of both hardware and software elements. Thus, while the description herein may describe certain embodiments, features, or components as being implemented in software or hardware, it should be recognized that any embodiment, feature, or component that is described in the present application may be implemented in hardware and/or software.
-
FIG. 1 is a block diagram of asystem 100 in accordance with certain embodiments. Thesystem 100 includes ameasurement device 150, which includeselectrodes 140 and atemperature measurement component 170 that are immersed in atest fluid 160. As an example, thetest fluid 160 can be a liquid or a gas. Thesystem 100 further includes a computing device(s) 110, awater management system 180, and anoxidizer generator 120. Thecomputing device 110, themeasurement device 150, thewater management system 180, and theoxidizer generator 120 can be in indirect communication with each other over anetwork 130 and/or in direct communication with each other. Thenetwork 130 may represent any type of communication network, e.g., such as one that comprises a local area network (e.g., a Wi-Fi network), a personal area network (e.g., a Bluetooth network), a wide area network, an intranet, the Internet, a cellular network, and/or other types of networks. AlthoughFIG. 1 may depict a single one of each ofcomputing device 110,measurement device 150,water management system 180, andoxidizer generator 120, it should be understood this is not intended to be limiting, and the system can include any number of each component (e.g.,computing devices 110,measurement devices 150,water management systems 180, and oxidizer generators 120) and sub-component (e.g.,electrodes 140 and multiple temperature measurement components 170), and all of the components and sub-components can be configured to communicate with each other directly or indirectly. - All the components illustrated in
FIG. 1 , including thecomputing device 110, themeasurement device 150, thewater management system 180, and theoxidizer generator 120 can be configured to communicate directly with each other and/or over thenetwork 130 via wired or wireless communication links, or a combination of the two. Each of thecomputing device 110, themeasurement device 150, thewater management system 180, and theoxidizer generator 120, can include one or more communication devices. The communication devices can include any device for communicating over a wired and/or wireless communication channel or communication link. In certain embodiments, communication devices can include one or more of the following: transceivers, transmitters, receivers, communication cards, network connectors, network adapters, and/or integrated circuits. Other types of communication devices also can be used. In certain embodiments, thecomputing devices 110 may represent desktop computers, laptop computers, mobile devices (e.g., smart phones, personal digital assistants, tablet devices, or any other devices that are mobile in nature), and/or other types of computing devices. - Each of the
computing device 110, themeasurement device 150, thewater management system 180, and theoxidizer generator 120 also can be equipped with one or more computer storage devices and one or more processing devices that are capable of executing computer program instructions. The computer storage devices may be physical, non-transitory mediums in certain embodiments. The one or more storage devices can communicate with the one or more processors, and the one or more processors can execute any instructions stored on the one or more storage devices. The one or more storage devices may include: i) non-volatile memory, such as, for example, read only memory (ROM) or programmable read only memory (PROM); and/or (ii) volatile memory, such as, for example, random access memory (RAM), dynamic RAM (DRAM), static RAM (SRAM), etc. In certain embodiments, the one or more storage devices can comprise (i) non-transitory memory and/or (ii) transitory memory. The one or more processors can include one or more central processing units (CPUs), controllers, microprocessors, digital signal processors, and/or computational circuits. - Embodiments or aspects of the techniques described herein may include a computer program product accessible from a computer-usable or computer-readable medium providing program code for use by or in connection with a computer or any instruction execution system. A computer-usable or computer-readable medium may include any apparatus that stores, communicates, propagates, or transports the program for use by or in connection with the instruction execution system, apparatus, or device. The medium can be a magnetic, optical, electronic, electromagnetic, infrared, or semiconductor system (or apparatus or device) or a propagation medium. The medium may include a computer-readable storage medium, such as a semiconductor or a solid state memory, a magnetic tape, a removable computer diskette, a random access memory (RAM), a read-only memory (ROM), a rigid magnetic disk, and an optical disk.
- The
measurement device 150 can be utilized to make a variety of different measurements. In certain exemplary embodiments, themeasurement device 150 can use water electrolysis to measure oxidizingcompounds 165 in water, such as drinking water and/or other types of water, using oxidation reduction potential (ORP) measurement techniques. In other exemplary embodiments, themeasurement device 150 can use electrolysis to take pH measurements, ion concentration measurements, potentiometric measurements, and/or other measurements. - According to certain embodiments, the
measurement device 150 includes at least threeelectrodes 140. Each of theelectrodes 140 can be constructed of a noble metal, a passivated transition metal, or a glass-like carbon (also referred to as “glassy carbons” or “vitreous carbons”). In certain embodiments, the electrodes are constructed of gold, platinum, titanium, or a glass-like carbon, or of some combination thereof. The electrodes can additionally, or alternatively, be constructed of other similar metals, compounds, or other materials that do not oxidize under the conditions applied to themeasurement device 150 when the measurement device is submerged in thetest fluid 160. Using such construction materials avoids the risk of corrosion, which can reduce the lifetime of themeasurement device 150, elute ions into the test fluid, and cause themeasurement device 150 to be insensitive to the oxidizingcompounds 165 being measured. - Two of the
electrodes 140 can be configured on a circuit as a reference pair, and a third one of theelectrodes 140 can be used as a sensor electrode. The sensor electrode may not be included on the circuit with the reference pair. When theelectrodes 140 of themeasurement device 150 are submerged in atest fluid 160 and a constant current is applied to the reference pair ofelectrodes 140, electrolysis will split the molecules of thetest fluid 160, and the electrochemical potential at which electrolysis occurs can be used as a reference voltage. In embodiments in which thetest fluid 160 is water, the reference pair electrolyzes the water to split the molecules into hydrogen and oxygen. For example, the reference electrodes can conduct water oxidation and/or water reduction and, therefore, evolve oxygen gas or hydrogen gas. In certain embodiments, the constant current that is applied is 10 microamperes (uA). - The
electrode 140 that is used as sensor electrode can be connected to one of theelectrodes 140 included in the reference pair using a high impedance resistor, an operational amplifier, and/or another component. By measuring the voltage across this connection, the voltage difference between the reference electrodes and the sensor electrode can be calculated. As oxidizingcompounds 165 are added to the test fluid 160 (e.g., to sanitize the test fluid 160), the potential on the sensor electrode will increase, and the measured voltage between the reference pair and the sensor electrode will change. Because this change is relative to the concentration of the oxidizingcompounds 165, the voltage measurement can be calibrated as an oxidizer concentration measurement (e.g., Vac inFIG. 2 ) that indicates the amount of oxidizingcompounds 165 in thetest fluid 160. - In certain embodiments, one of the
electrodes 140 included in the reference pair can measure a voltage indicating an electrochemical potential at which electrolysis occurs in thetest liquid 160, and the sensor electrode can measure a voltage indicating an oxidizing potential of thetest fluid 160. Themeasurement device 150 can then subtract the voltage measured by the sensor electrode from the voltage measured by theelectrode 140 included in the reference pair to calculate the oxidizer concentration measurement. - According to certain embodiments, the
measurement device 150 also can be configured to execute a self-cleaning function on theelectrodes 140. During normal operation (e.g., when themeasurement device 150 is operating in a potentiometric mode and is being utilized to measure and/or control levels of oxidizingcompounds 165 in the test fluid 160), the surface of theelectrodes 140 may be reduced, thereby causing a gain in electrons. To combat this reduction, which occurs during normal operation, themeasurement device 150 also can be operated in a reverse polarization mode that executes the self-cleaning function. During use in the reverse polarization mode, themeasurement device 150 utilizes an H-bridge, or other equivalent electrical component, to reverse the current that is applied to the reference pair ofelectrodes 140. This reversal of the current can produce a redox (or reduction-oxidation) reaction on the reference pair ofelectrodes 140, which is inverse to that current used during normal operation and which reverses the reduction by oxidizing the surface of theelectrodes 140. - The
measurement device 150 also can take measurements of the oxidizingcompounds 165 when operating in the chronopotentiometric mode. In some embodiments, the measurements taken by themeasurement device 150 in the chronopotentiometric mode can be used to confirm the accuracy of the measurements taken by themeasurement device 150 in the normal or potentiometric mode. To deduce oxidizer concentration measurements, themeasurement device 150 can short one or more of theelectrodes 140 to an electrical ground, which can have the effect of applying a reducing potential toelectrodes 140 and purging the surface of the electrode of oxidizingcompounds 165 by a process of electrochemical reduction. The concentration of the oxidizingcompounds 165 may be deduced by measuring both the maximum voltage and the time to reach that maximum voltage. As the recovery time will be shortened with increases in concentration of oxidizingcompounds 165, a chronopotentiometric measurement of oxidizer concentration can be ascertained. - According to certain embodiments, the
measurement device 150 can include afourth electrode 140, which also is constructed of a noble metal, a passivated transition metal, a glass-like carbon, and/or some combination thereof. Thisfourth electrode 140 can be paired with the sensor electrode, thus allowing either pair of electrodes to be used as a reference pair in taking measurements and/or to implement the self-cleaning procedure. It should be noted that thefourth electrode 140 is optional, and themeasurement device 150 is capable of functioning without the inclusion of thefourth electrode 140. - According to certain embodiments, the
measurement device 150 can include atemperature measurement component 170 that is configured to measure or determine the temperature of thetest fluid 160. Thetemperature measurement component 170 can include a thermistor and/or other device that is capable of measuring the temperature of thetest fluid 160. The temperature readings generated by thetemperature measurement component 170 can be used by themeasurement device 150, along with other data (e.g., oxidizer concentration measurements) to adjust and/or control (e.g., to increase or decrease) the concentration of the oxidizingcompounds 165 in thetest fluid 160. - The
measurement device 150 can be used to detect and/or measure oxidizingcompounds 165 invarious test fluids 160. In certain embodiments, thetests liquids 160 can include water, (e.g., drinking water, non-potable water, distilled water, deionized water, and/or other types of water). Thetests liquids 160 can additionally, or alternatively, include alcohols (e.g., ethanol, methanol, and other alcohols) and/or electrolyze-able organic solvents (e.g., acetic acid). - In certain embodiments, the
measurement device 150 can be used to detect and measure microbial life in test fluids 160 (e.g., water). For example, as aerobic microbial life consumes oxygen in order to live and propagate, a concentration of microbes in atest fluid 160 can reduce the oxidizing compounds 165. This reduction of oxidizingcompounds 165 in thetest fluid 160 can therefore be used to measure the microbial life content. - The
measurement device 150 can be used to detect and measure various types of oxidizingcompounds 165. Such oxidizingcompounds 165 can include, but are not limited to, any or all of the following: oxygen (O2), ozone (O3), hydrogen peroxide (H2O2) (as well as other inorganic peroxides), fluorine (F2), chlorine (Cl2), halogen compounds, nitric acid (HNO3), nitrate compounds, sulfuric acid (H2SO4), peroxydisulfuric acid (H2S2O8), peroxymonosulfuric acid (H2SO5), chlorite, chlorate, perchlorate, hypochlorite (and other hypohalite compounds), household bleach (NaClO), hexavalent chromium compounds (e.g., chromic and dichromic acids and chromium trioxide, pyridinium chlorochromate, and chromate/dichromate compounds), permanganate compounds (e.g., potassium permanganate), sodium perborate, nitrous oxide (N2O), nitrogen dioxide (NO2), dinitrogen tetroxide (N2O4), potassium nitrate (KNO3), and/or sodium bismuthate. - In certain embodiments, the
measurement device 150 also can be used to detect and measure various types of reducing compounds. Such reducing compounds can include, but are not limited to, any or all of the following: hydrogen, diborane, sodium borohydride (NaBH4), sulfur dioxide, sulfite compounds, dithionates (e.g., Na2S2O6), thiosulfates (e.g., Na2S2O3), iodides (e.g., KI), hydrazine, diisobutylaluminium hydride (DIBAL-H), oxalic acid, formic acid (HCOOH), ascorbic acid (C6H8O6), reducing sugars, phosphites, hypophosphites, phosphorous acid, dithiothreitol (DTT), carbon monoxide (CO), cyanides, carbon (C), tris-2-carboxyethylphosphine hydrochloride (TCEP), compounds containing the Fe2+ ion (e.g., such as iron(II) sulfate), and/or compounds containing the Sn2+ ion (e.g., such as tin(II) chloride). - In certain embodiments, the
measurement device 150 can be incorporated into awater management system 180. Thewater management system 180 can include any system, device, and/or apparatus that produces, generates, stores, manages, and/or distributes drinking water and/or other types of water. For example, themeasurement device 150 can be incorporated into awater management system 180 that produces or generates liquid water by extracting water vapor from ambient air or atmospheric air. In certain embodiments, themeasurement device 150 and/or related techniques described herein can be utilized in connection with the systems, methods, and apparatuses described in: (i) U.S. patent application Ser. No. 15/482,104 filed on Apr. 7, 2017 (U.S. Patent Publication No. 2017-0294876) entitled “SOLAR THERMAL UNIT”; (ii) U.S. patent application Ser. No. 15/600,046 filed on May 19, 2017 (U.S. Patent Publication No. 2018-0043295) entitled “SYSTEMS AND METHODS FOR WATER EXTRACTION CONTROL”; (iii) International Patent App. No. PCT/US18/49411 filed on Sep. 4, 2018 entitled “SYSTEMS AND METHODS FOR MANAGING PRODUCTION AND DISTRIBUTION OF LIQUID WATER EXTRACTED FROM AIR”; (iv) International Patent App. No. PCT/US18/49398 filed on Sep. 4, 2018 entitled “SYSTEMS AND METHODS TO PRODUCE LIQUID WATER EXTRACTED FROM AIR”; (v) International Patent App. No. PCT/US18/42098 filed on Jul. 13, 2018 entitled “SYSTEMS FOR CONTROLLED TREATMENT OF WATER WITH OZONE AND RELATED METHODS THEREFOR”; and/or (vi) International Patent App. No. PCT/US15/61921 filed on Nov. 20, 2017 entitled “SYSTEMS AND METHODS FOR GENERATING LIQUID WATER FROM AIR.” Each of the aforementioned disclosures is herein incorporated by reference in its entirety. Themeasurement device 150 and/or techniques described herein can be used in connection with other types of water management systems as well. - In such water management systems or in other systems, the
test fluid 160 can be water and the oxidizing compounds 165 (e.g., ozone) can be applied to water in order to sanitize the water and make it safe for consumption. Themeasurement device 150 described herein can be configured to measure the concentration of the oxidizingcompounds 165 in the water to ensure that a sufficient amount of the oxidizingcompounds 165 has been applied to sterilize the water and/or to ensure that the water is safe for drinking. - The
oxidizer generator 120 can be any device or apparatus that is configured to generate and/or apply oxidizingcompounds 165 to thetest fluid 160. For example, in certain embodiments (e.g., such as those in which thetest fluid 160 comprises water), theoxidizer generator 120 can include an ozone generator that is configured to generate and apply ozone to sterilize water or other test fluids. Theoxidizer generator 120 can additionally, or alternatively, be configured to generate and/or apply other types of oxidizingcompounds 165 to the test fluid, including any of the oxidizingcompounds 165 mentioned in this disclosure. In certain embodiments, the measurements taken by themeasurement device 150 can be used to control (e.g., to increase or decrease) the concentration of the oxidizingcompounds 165 in thetest fluid 160. In certain embodiments, theoxidizer generator 120 may be integrated with thewater management system 180 to control the concentration of the oxidizingcompounds 165 intest fluids 160 that include water. - As mentioned above, the
measurement device 150 can be used intesting liquids 160 other than water and can take a variety of different measurements. For example, in certain embodiments, theelectrodes 140 included in themeasurement device 150 can include one or more pH electrodes and/or proton selective electrodes that enable themeasurement device 150 to apply electrolysis to thetest fluid 160 for taking pH measurements, acid concentration measurements, base measurements, and/or the like. Alternatively, or additionally, theelectrodes 140 of themeasurement device 150 can include one or more ion selective electrodes (ISE) that enable themeasurement device 150 to apply electrolysis to thetest fluid 160 for taking ion concentration measurements. - In certain embodiments, the
measurement device 150 and/orwater management system 180 implements a control function for regulating the concentration of the oxidizingcompounds 165 in thetest fluid 160. For example, in certain embodiments, themeasurement device 150 and/orwater management system 180 may regulate the concentration of ozone that is applied to disinfect or sterilize water to ensure that the water is potable and safe for consumption. The control function may be implemented using one or more processors (e.g., one or more microcontrollers) integrated into themeasurement device 150 and/orwater management system 180. The control function can activate theoxidizer generator 120 if the voltage indicating the oxidizer or ozone concentration measurement reaches a first specified threshold (e.g., indicating that ozone should be applied to reduce the concentration of microbial life in the water), and can deactivate theoxidizer generator 120 if the voltage indicating the oxidizer or ozone concentration measurement reaches a second specified threshold (e.g., indicating the current concentration of ozone is sufficient and/or that the water is safe for consumption). - In certain embodiments, in response to reaching the second threshold, the control function implements a timeout (e.g., 5 minutes, 10 minutes, 15 minutes, or 1 hour) during which the
measurement device 150 does not take measurements and theoxidizer generator 120 does not apply oxidizingcompounds 165. In certain embodiments, the control function can be configured to execute a closed loop control technique, in which themeasurement device 150 will cause theoxidizer generator 120 to apply ozone to maintain a predefined ozone voltage measurement, and will cut off power to themeasurement device 150 and/oroxidizer generator 120 when the voltage is registered as sufficient (e.g., when the voltage reaches the second threshold). - The
computing device 110 can be configured to access themeasurement device 150, theoxidizer generator 120, and/or thewater management system 180 to monitor and/or control various aspects of thesystem 100. For example, thecomputing device 110 can be configured to review measurements and other data generated by themeasurement device 150. Thecomputing device 110 also can be configured to transmit commands to themeasurement device 150, theoxidizer generator 120, and/or thewater management system 180 for switching between potentiometric and chronopotentiometric modes, executing the self-cleaning function, managing the control functions, adjusting concentrations of oxidizingcompounds 165 in thetest fluid 160, and/or performing other related functions. Thecomputing device 110 can be operated by an administrator or other individual who is associated with managing themeasurement device 150 and/orwater management system 180. - The embodiments described herein provide a variety of advantages over conventional measurement devices and probes. Some of the advantages include the ability to extend the lifetime of the
measurement device 150 and to increase the reliability of any measurements taken using themeasurement device 150. This can be attributed, at least in part, to the structure of themeasurement device 150, which utilizes noble metals, passivated transition metals, and/or glassy carbons for theelectrodes 140 immersed in thetest fluid 160, and the electrolysis-based techniques utilized to take the measurements. Another significant advantage is the ability of themeasurement device 150 to operate in a reverse polarization mode that allows themeasurement device 150 to self-clean the surfaces of theelectrodes 140. A further advantage of the device is the ability to operate in a chronopotentiometric mode to take measurements that can be used to confirm the measurements taken during normal operation. This technology-based solution marks an improvement over existing measurement devices and probes. -
FIG. 2 is a circuit diagram of acontrol board 200 that may be utilized by a measurement device (e.g.,measurement device 150 inFIG. 1 ) in accordance with certain embodiments. In certain embodiments, thecontrol board 200 may be utilized for a measurement device that is assessing water and applying ozone as an oxidizing compound to sterilize the water. - The
control board 200 includes, inter alia, the following components: amicrocontroller 210, apower supply 220, an H-bridge 230, a MOSFET (metal-oxide-semiconductor field-effect transistor) 240, a pair ofresistors 250, and an operational amplifier (op amp) 260. In this exemplary embodiment, thepower supply 220 can be a 10 uA constant current supply, theMOSFET 240 can be an N-channel MOSFET, theop amp 260 can be a differential op amp, and theresistors 250 can be 30 megaohms (Mohms) resistors. In other embodiments, different types of components can be integrated into thecontrol board 200 based on the test fluid and/or based on the types of measurements that are being deduced. - The
control board 200 also includes three electrical connections—A, B, and C—for each of three connected electrodes (e.g.,electrodes 140 inFIG. 1 ). For example, in certain embodiments, the three electrical connections—A, B, and C—may be connected to wires, and the electrodes can be attached to the end of the wires and suspended in the test fluid. In this example, the electrodes corresponding to electrical connections A and B form the reference pair, and the electrical connection C corresponds to the sensor electrode. As explained above, in other embodiments, the measurement device may include a fourth electrode as well. In such embodiments, an additional electrical connection can be added to thecontrol board 200 to facilitate connection of the fourth electrode. The fourth node can be included on a circuit with the electrical connection C corresponding to the sensor electrode. T1 and T2 are electrical connections to a temperature measurement component (e.g.,temperature measurement component 170 inFIG. 1 ). - The
power supply 220 may be configured to regulate a fixed current by adjusting the output voltage as the load changes. A constant current power supply provides a regulated 1 or 10 pA of current ranging from 0 to 3 VDC (volts DC). The constant current supply may be implemented using an instrumentation operational amplifier. When the current is applied to electrodes A and B, the water or test fluid will be electrolyzed, and this circuit will be used to produce Vab, which is a measure of the test fluid conductivity, and Ref, which is a measure of the electrochemical potential at which electrolysis occurs in the test fluid. Under ideal conditions, water electrolysis occurs at ˜1.23 V (volts). However, Ref reflects the true voltage for performing electrolysis and, thus, can vary based on actual operating conditions (e.g., based on the separation distance of the electrodes). Electrode C measures a voltage indicating an oxidizing potential of the test fluid, which is shown as V0p. Ref and V0p are passed through theresistors 250 and supplied toop amp 260.Op amp 260 subtracts V0p from Ref to produce Vac, which serves as an indicator of the oxidation potential voltage. T1 is the electrical connection to the temperature measurement component and T2 is a connection to a ground associated with the temperature measurement component. Temp is a voltage indicating the temperature of the test fluid. - The
microcontroller 210 receives the following inputs: - (1) Vab: this is the water electrolysis cell voltage (Vab=A−B) and serves as an indicator of test fluid conductivity;
- (2) Vac: this is the oxidizer concentration measurement (in this case, an ozone concentration measurement) and serves as an indicator of the oxidation potential voltage (Vac=A−C);
- (3) Temp: this is a temperature measurement of the
test fluid 160 received from the temperature measurement component (e.g., thermistor); - (4) 3.3 V: this is the power supplied to the
control board 200; and - (5) SDA/SCL: these are I2C network signals between the
microcontroller 210 and a host controller. - The outputs of the
microcontroller 210 include: - (1) H-Bridge output signal: this output controls the current flow and instructs the H-Bridge whether the current should be reversed (e.g., depending upon whether not the device is operating in the normal mode or the reverse polarization mode);
- (2) MOSFET output signal: this output controls whether or not electrode C is connected to a ground by sending instructions to the MOSFET; and
- (3) SDA/SCL output signals: these outputs are provided as part of an I2C network and can communicate the electrode voltage measurements (Vab and Vac) as well as the temperature measurement (T1) upon request from the host controller.
- The
microcontroller 210 can use the electrode voltage measurements (Vab and Vac) as well as the temperature measurement (T1) to implement the control function for increasing and/or decreasing the concentration of ozone in the water. Themicrocontroller 210 can compare these parameters to a library of pre-stored conditions to activate and/or deactivate an ozone generation system. The library may be use the temp measurement, inter alia, to control the current that is applied to the test fluid and/or to control the oxidizing compounds that are applied to the test fluid. - As mentioned above, the measurement device can operate in a potentiometric mode (e.g., during normal operation when the concentration of the ozone or other oxidizing compound is being measured), a chronopotentiometric mode (e.g., during an operation that cleans the sensor electrode and/or takes confirmatory measurements), and a reverse polarity mode (e.g., during a self-cleaning operation that cleans the electrodes and/or takes confirmatory measurements). When operating in the potentiometric mode, the H-Bridge output signal provided by the
microcontroller 210 can instruct the H-Bridge 230 that the current flow is not to be reversed, and the MOSFET output signal can instructMOSFET 240 that theelectrode 140 corresponding to electrical connection C is not to be connected to a ground. When operating in reverse polarity mode, the H-Bridge output signal provided by themicrocontroller 210 can instruct the H-Bridge 230 that the current flow is to be reversed. When operating in chronopotentiometric mode the MOSFET output signal can instructMOSFET 240 that the electrode corresponding to electrical connection C is to be connected to a ground. Connecting to the ground will close the circuit between electrode C and the ground, and will result in a “purge” that is intended to reduce any residual oxidizer on the surface of the electrode. - The SDA/SCL connections connect the
microcontroller 210 to a host controller. In certain embodiments, themicrocontroller 210 acts as a “slave” device and communicates the electrode voltage measurements and temperature measurements upon request from the host controller. Themicrocontroller 210 also can receive commands from the host controller for controlling the H-bridge 230 for electrodes A and B, and the MOSFET 240 (e.g., which may be an N-channel MOSFET) for electrode C. -
FIG. 3 is a diagram 300 illustrating how measurements are computed in accordance with certain embodiments. This diagram illustrates how measurements may be computed by the measurement device (e.g.,measurement device 150 inFIG. 1 ) for various embodiments in which ozone concentration is being measured in water. - The axis on the left represents a range of possible voltages associated with the electrochemical potential at which the process of water electrolysis occurs. This axis is not labeled because the values may be dependent on the type of electrodes that are used. The bracket labeled “Water Electrolysis Voltage 1.23V” represents the voltage to perform water electrolysis under standard conditions. On the far right side, there is a bracket labeled “Cell voltage” that represents the measurement of voltage used to conduct water electrolysis, which considers all features of the true voltage measurement (e.g., such as the area of the
test fluid 160 and the distance or separation of the electrodes). - The “Over potentials” for the reference electrodes represent the difference between the cell voltage and the standard water electrolysis voltage. The electrochemical reactions for water electrolysis also are listed in the figure. An ozone voltage is a function of ozone concentration and can be any value in a range that falls within the water electrolysis reaction voltages. The difference between this voltage and the voltage of the reference is reported as the oxidation potential measurement. In certain embodiments, the reference electrodes are conducting water oxidation and, therefore, are evolving oxygen gas. The reference electrodes can additionally, or alternatively, conduct water reduction and, therefore, evolve hydrogen gas.
- Turning ahead in the drawings,
FIGS. 4-6 illustrate flow charts forexemplary methods Methods Methods methods methods methods FIG. 1 ) and/or measurement device 150 (FIG. 1 ) can be suitable to performmethods methods methods FIG. 1 ), measurement device 150 (FIG. 1 ) and/or control board 200 (FIG. 2 ). The processor(s) can be similar or identical to the processor(s) described above with respect to system 100 (FIG. 1 ). -
FIG. 4 is a flow chart of anexemplary method 400 in accordance with certain embodiments.Method 400 can comprise anactivity 410 of applying a constant current to a test fluid including an oxidizing compound.Method 400 can further comprise anactivity 420 of measuring a reference voltage indicating an electrochemical potential at which electrolysis occurs in the test fluid.Method 400 can further comprise anactivity 430 of measuring a second voltage indicating an oxidizing potential of the test fluid.Method 400 can further comprise anactivity 440 of calculating an oxidizer concentration measurement indicating the concentration of the oxidizing compound in the test fluid based on a voltage difference between the reference voltage and the second voltage. As an example, one of or both ofsystem 100 inFIG. 1 andcontrol board 200 inFIG. 2 can be used to perform some or all of one or more ofactivities -
FIG. 5 is a flow chart of a secondexemplary method 500 in accordance with certain embodiments.Method 500 can comprise anactivity 510 of submerging electrodes, including at least a pair of reference electrodes and a sensor electrode in a test fluid that includes oxidizing compounds.Method 500 can further comprise anactivity 520 of applying a constant current to the pair of reference electrodes submerged in the test fluid.Method 500 can further comprise anactivity 530 of measuring a conductivity or electrical resistance of the test fluid based on the constant current using the sensor electrode.Method 500 can further comprise anactivity 540 of measuring an oxidation potential voltage of the test fluid using the pair of reference electrodes.Method 500 can further comprise anactivity 550 of measuring a temperature of the test fluid using a temperature measurement component.Method 500 can further comprise anactivity 560 of using the measurements to control an oxidizer generation system that is able to apply oxidizing compounds to the test fluid. As an example, one of or both ofsystem 100 inFIG. 1 andcontrol board 200 inFIG. 2 can be used to perform some or all of one or more ofactivities -
FIG. 6 is a flow chart of a thirdexemplary method 600 in accordance with certain embodiments.Method 600 can comprise anactivity 610 of submerging electrodes, including at least a pair of reference electrodes and a sensor electrode in a test fluid that comprises water and ozone.Method 600 can further comprise anactivity 620 of applying a constant current to the pair of reference electrodes submerged in the test fluid.Method 600 can further comprise anactivity 630 of measuring, using the sensor electrode, a conductivity or electrical resistance of the test fluid based on the constant current.Method 600 can further comprise anactivity 640 of measuring, using the pair of reference electrodes, an ozone oxidation potential voltage.Method 600 can further comprise anactivity 650 of measuring, using a temperature measurement component, a temperature of the test fluid.Method 600 can further comprise anactivity 660 of utilizing the measurements to control an ozone generation system that is able to apply ozone to the test fluid. As an example, one of or both ofsystem 100 inFIG. 1 andcontrol board 200 inFIG. 2 can be used to perform some or all of one or more ofactivities - Although systems and methods have been described with reference to specific embodiments, it will be understood by those skilled in the art that various changes may be made without departing from the spirit or scope of the disclosure. Accordingly, the disclosure of embodiments is intended to be illustrative of the scope of the disclosure and is not intended to be limiting. It is intended that the scope of the disclosure shall be limited only to the extent required by the appended claims. For example, to one of ordinary skill in the art, it will be readily apparent that any element of
FIGS. 1-6 may be modified, and that the foregoing discussion of certain of these embodiments does not necessarily represent a complete description of all possible embodiments. For example, one or more of the procedures, processes, and/or activities ofFIGS. 4-6 may include different procedures, processes, and/or activities and be performed by many different modules and/or components, in many different orders. - All elements claimed in any particular claim are essential to the embodiment claimed in that particular claim. Consequently, replacement of one or more claimed elements constitutes reconstruction and not repair. Additionally, benefits, other advantages, and solutions to problems have been described with regard to specific embodiments. The benefits, advantages, solutions to problems, and any element or elements that may cause any benefit, advantage, and/or solution to occur or become more pronounced, however, are not to be construed as critical, required, or essential features or elements of any or all of the claims, unless such benefits, advantages, solutions, and/or elements are stated in such claim.
- Moreover, embodiments and limitations disclosed herein are not dedicated to the public under the doctrine of dedication if the embodiments and/or limitations: (1) are not expressly claimed in the claims; and (2) are, or potentially are, equivalents of express elements and/or limitations in the claims under the doctrine of equivalents.
Claims (21)
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US11913903B1 (en) | 2024-02-27 |
WO2020086621A1 (en) | 2020-04-30 |
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US20200209190A1 (en) | 2020-07-02 |
AU2019364339A1 (en) | 2021-06-10 |
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US20230014032A1 (en) | 2023-01-19 |
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