A heat exchange controller, system, method, electronic device, and storage medium for titration calorimetry

Abstract

This application discloses a heat exchange controller, system, method, electronic device, and storage medium for titration calorimetry. The heat exchange controller includes: a heat exchange unit; a temperature monitoring unit; and a control unit. The control unit is electrically connected to the heat exchange unit and the temperature monitoring unit. The control unit is used to continuously monitor the temperature of the reaction system through the temperature monitoring unit and repeatedly perform the following operations until a preset termination condition is reached: acquiring a temperature baseline value through the temperature monitoring unit, the temperature baseline value being the temperature of the reaction system in thermal equilibrium before the titration operation; performing the titration operation after the temperature baseline value is acquired; starting the heat exchange unit to exchange heat with the reaction system after the titration reaction ends; and controlling the heat exchange unit to stop heat exchange when the temperature of the reaction system recovers to a threshold range based on the temperature baseline value, i.e., when the reaction system is in a "quasi-isothermal" state.

Description

Technical Field

[0001] This application relates to the field of microcalorimetry, and in particular to a heat exchange controller, system, method, electronic device and storage medium for titration calorimetry. Background Technology

[0002] The constant-temperature environment automatic titration calorimeter achieves excellent temperature isolation by encasing the calorimetric chamber in a constant-temperature solution. An automatic titration system completes operations such as liquid aspiration, titration, and cleaning, improving the automation level of titration calorimetry. The device includes a heat exchanger inside the calorimetric container to accelerate the system temperature recovery after the titration reaction, thereby shortening the waiting time between titrations.

[0003] However, existing automated titration calorimeters in constant-temperature environments use heat exchangers consisting only of a U-shaped glass tube, a solenoid valve, and a submersible pump. They employ open-loop control, meaning start-up and shutdown timing rely entirely on manual judgment. In practice, operators rely on visual observation of the temperature curve, making it difficult to accurately pinpoint the temperature recovery endpoint. This frequently leads to temperature overshoot or insufficient recovery, preventing the system temperature from accurately returning to the pre-reaction baseline. Even if the titration system allows for continuous liquid addition, natural thermal equilibrium must be awaited after each titration, hindering continuous measurement. Data from each titration can only be stored in segments (e.g.,...). Figure 1 As shown in the figure, this limits the application of the device in thermodynamic research. Summary of the Invention

[0004] This application aims to provide a heat exchange controller, system, method, electronic device, and storage medium for titration calorimetry, which enables continuous measurement of titration data.

[0005] In a first aspect, embodiments of this application provide a heat exchange controller, including: A heat exchange unit, wherein the heat exchange unit is used to exchange heat with the reaction system; A temperature monitoring unit, which is used to monitor the temperature of the reaction system in real time; A control unit, electrically connected to the heat exchange unit and the temperature monitoring unit, is used to continuously monitor the temperature of the reaction system through the temperature monitoring unit after the reaction system is placed in a constant temperature environment, and repeatedly perform the following operations until a preset termination condition is reached to obtain a temperature data sequence: The temperature baseline value is collected by the temperature monitoring unit. The temperature baseline value is the temperature value of the reaction system in thermal equilibrium state before the titration operation. After the temperature baseline value is acquired, a titration operation is performed to carry out the titration reaction; Upon completion of the titration reaction, the heat exchange unit is activated to exchange heat with the reaction system. When the temperature of the reaction system recovers to a threshold range based on the temperature baseline, i.e., when the reaction system is in a "quasi-isothermal" state, the heat exchange unit is controlled to stop heat exchange.

[0006] According to some embodiments of this application, the heat exchange unit includes: A heat exchange tube, wherein the heat exchange tube is placed within the reaction system; A pump connected to the heat exchange tube is used to draw a constant temperature medium from the constant temperature environment and drive the constant temperature medium to flow through the heat exchange tube. When the pump is turned off, the residual amount of the constant temperature medium in the heat exchange tube remains constant.

[0007] According to some embodiments of this application, the pump is a peristaltic pump.

[0008] According to some embodiments of this application, the heat exchange tube is a spiral heat exchange tube or a U-shaped heat exchange tube.

[0009] Secondly, embodiments of this application provide a titration calorimetry system, comprising: titration calorimetry apparatus; And a heat exchange controller as described in any of the preceding claims, wherein the heat exchange unit of the heat exchange controller is disposed within the reaction system of the titration calorimeter, and the temperature monitoring unit of the heat exchange controller is disposed within the reaction system.

[0010] Thirdly, embodiments of this application provide a titration calorimetry method applied to a heat exchange controller as described above, the method comprising: The reaction system was placed in a constant temperature environment; The temperature of the reaction system is continuously monitored by a temperature monitoring unit, and the following operation is repeated until the preset termination condition is reached to obtain a temperature data sequence: The temperature baseline value is collected by the temperature monitoring unit. The temperature baseline value is the temperature value of the reaction system in thermal equilibrium state before the titration operation. After the temperature baseline value is acquired, a titration operation is performed to carry out the titration reaction; Upon completion of the titration reaction, the heat exchange unit is activated to perform heat exchange on the reaction system. When the temperature of the reaction system recovers to a threshold range based on the temperature baseline, i.e., when the reaction system is in a "quasi-isothermal" state, the heat exchange unit is controlled to stop heat exchange.

[0011] According to some embodiments of this application, the heat exchange unit includes a heat exchange tube and a pump, wherein the heat exchange tube is placed within the reaction system and the pump is connected to the heat exchange tube; The starting heat exchange unit performs heat exchange on the reaction system, including: The pump is started to draw the constant temperature medium from the constant temperature environment and drive the constant temperature medium to flow through the heat exchange tube to exchange heat with the reaction system.

[0012] According to some embodiments of this application, controlling the heat exchange unit to stop heat exchange includes: The pump is shut down to keep the residual amount of the isothermal medium in the heat exchange tube constant.

[0013] Fourthly, embodiments of this application provide an electronic device, including: At least one processor; At least one memory for storing at least one program; The titration calorimetry method described above is implemented when at least one of the programs is executed by at least one of the processors.

[0014] Fifthly, embodiments of this application provide a computer-readable storage medium storing a processor-executable program, which, when executed by a processor, is used to implement the titration calorimetry method as described above.

[0015] In this embodiment, a closed-loop feedback control system is constructed by setting up a heat exchange unit, a temperature monitoring unit, and a control unit electrically connected to them. The control unit, after the reaction system is placed in a constant-temperature environment, first continuously monitors the temperature of the reaction system through the temperature monitoring unit, and collects the temperature baseline value of the reaction system when it is in thermal equilibrium before each titration, thereby establishing a precise temperature reset benchmark. During the titration reaction, the control unit does not activate the heat exchange unit, allowing the temperature of the reaction system to change naturally, thus fully recording the reaction heat effect. After the titration reaction is completed, the control unit immediately activates the heat exchange unit to actively exchange heat with the reaction system, and during this period, monitors the temperature of the reaction system in real time through the temperature monitoring unit until it accurately recovers to the threshold range based on the temperature baseline value collected before titration, that is, when the reaction system is in a "quasi-isothermal" state, the control unit shuts down the heat exchange unit, completing a complete temperature reset process. By repeating the above operations until the preset termination condition is reached, each titration reaction can be carried out under almost identical initial temperature conditions. This effectively eliminates problems such as temperature overshoot, insufficient temperature recovery, and system heat capacity fluctuations caused by open-loop control and manual operation in traditional constant-temperature titration calorimeters. It truly realizes continuous measurement in the continuous titration process, allowing the temperature data from multiple titrations to be recorded as a single continuous temperature data sequence. This significantly improves the automation level, data continuity, and reliability of measurement results in titration calorimetry experiments, providing a more precise experimental method for thermodynamic research.

[0016] Additional aspects and advantages of this application will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of this application. Attached Figure Description

[0017] The present application will be further described below with reference to the accompanying drawings and embodiments, wherein: Figure 1 The graph shows the temperature versus time relationship in the titration reaction of hydrochloric acid with THAM using the AMM method. Figure 2 A schematic diagram of an embodiment of the heat exchange controller provided in this application; Figure 3 A temperature versus time curve of the titration reaction is provided in the embodiment of the heat exchange controller provided in this application; Figure 4 A flowchart of the titration process control in the embodiment of the heat exchange controller provided in this application; Figure 5 In the embodiment of the heat exchange controller provided in this application, the thermoelectric potential curve of the hydrochloric acid-THAM titration reaction was measured using a continuous testing mode. Figure 6A schematic diagram of an embodiment of the electronic device provided in this application.

[0018] Figure label: Titration control system 100, temperature acquisition module 200, microcontroller 210, multiplex analog switch 220, constant current source 230, reference resistor 240, variable gain amplifier 250, low dropout linear regulator 260, 24-bit analog-to-digital converter 270, RS485 communication interface 280, temperature sensor 300, peristaltic pump 400, heat exchange tube 500, silicone tubing 600, Dewar reaction cell 700, thermostatic bath 800, electronic equipment 900, processor 910, memory 920. Detailed Implementation

[0019] The embodiments of this application are described in detail below. Examples of these embodiments are shown in the accompanying drawings, wherein the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions throughout. The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain this application, and should not be construed as limiting this application.

[0020] In the description of this application, it should be understood that the orientation descriptions, such as up, down, etc., are based on the orientation or positional relationship shown in the accompanying drawings, and are only for the convenience of describing this application and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of this application.

[0021] In the description of this application, "multiple" refers to two or more. The use of "first" and "second" is for the purpose of distinguishing technical features only and should not be construed as indicating or implying relative importance, or implicitly indicating the number of technical features indicated, or the order in which the technical features are indicated.

[0022] In the description of this application, unless otherwise expressly defined, terms such as "setup," "installation," and "connection" should be interpreted broadly, and those skilled in the art can reasonably determine the specific meaning of the above terms in this application in conjunction with the specific content of the technical solution.

[0023] The following is based on Figures 1 to 6 This application describes a heat exchange controller, system, method, electronic device, and storage medium for titrating calorimetry, provided by embodiments of the present application.

[0024] This application provides a heat exchange controller, including: The heat exchange unit is used for heat exchange with the reaction system; Temperature monitoring unit, used to monitor the temperature of the reaction system in real time; The control unit is electrically connected to the heat exchange unit and the temperature monitoring unit. After the reaction system is placed in a constant-temperature environment, the control unit continuously monitors the temperature of the reaction system via the temperature monitoring unit and repeats the following operations until the preset termination condition is reached, obtaining a temperature data sequence: The temperature baseline value is collected by the temperature monitoring unit. The temperature baseline value is the temperature value of the reaction system in thermal equilibrium before the titration operation. After the temperature baseline value is collected, a titration operation is performed to carry out the titration reaction; After the titration reaction is complete, the heat exchange unit is activated to exchange heat with the reaction system. When the temperature of the reaction system recovers to a threshold range based on the temperature baseline, i.e., when the reaction system is in a "quasi-isothermal" state, the heat exchange unit stops heat exchange.

[0025] In this embodiment, a closed-loop feedback control system is constructed by setting up a heat exchange unit, a temperature monitoring unit, and a control unit electrically connected to them. The control unit, after the reaction system is placed in a constant-temperature environment, first continuously monitors the temperature of the reaction system through the temperature monitoring unit, and collects the temperature baseline value of the reaction system when it is in thermal equilibrium before each titration, thereby establishing a precise temperature reset benchmark. During the titration reaction, the control unit does not activate the heat exchange unit, allowing the temperature of the reaction system to change naturally, thus fully recording the heat effect of the reaction. After the titration reaction is completed, the control unit immediately activates the heat exchange unit to actively exchange heat with the reaction system, and during this period, monitors the temperature of the reaction system in real time through the temperature monitoring unit until it returns to the threshold range based on the temperature baseline value collected before titration. Then, the control unit shuts down the heat exchange unit, completing a complete temperature reset process. By repeating the above operations until the preset termination condition is reached, each titration reaction can be carried out under almost identical initial temperature conditions. This effectively eliminates problems such as temperature overshoot, insufficient temperature recovery, and system heat capacity fluctuations caused by open-loop control and manual operation in traditional constant-temperature titration calorimeters. It truly realizes continuous measurement in the continuous titration process, allowing the temperature data from multiple titrations to be recorded as a single continuous temperature data sequence. This significantly improves the automation level, data continuity, and reliability of measurement results in titration calorimetry experiments, providing a more precise experimental method for thermodynamic research.

[0026] The aforementioned preset termination condition can be a preset number of titrations, such as 10. However, the preset termination condition is not limited to a preset number of titrations; operators can flexibly set other preset termination conditions according to experimental needs. For example, when the rate of change of the reaction heat value measured in several consecutive titrations is lower than a preset threshold, the reaction can be considered to have reached equilibrium, thus automatically terminating the titration, suitable for scenarios where the substrate is exhausted or the reaction is nearing completion; it can also automatically terminate the experiment to protect the instrument and data validity when the temperature baseline drift between two consecutive titrations exceeds a preset range; a total experimental time limit can also be set, automatically ending the titration process when the duration reaches a preset value; in addition, operators can send a stop command through the control interface at any time based on experimental observations to achieve manual intervention and termination. The preset threshold range based on the temperature baseline value can be set according to the experimental accuracy requirements, for example, it can be set within ±0.001℃ of the temperature baseline value.

[0027] In some embodiments of this application, the heat exchange unit includes: Heat exchange tube 500 is placed inside the reaction system; A pump is connected to a heat exchange tube 500. The pump is used to extract a constant temperature medium from a constant temperature environment and drive the constant temperature medium to flow through the heat exchange tube 500. When the pump is turned off, the residual amount of constant temperature medium in the heat exchange tube 500 remains constant.

[0028] In this embodiment, by connecting the pump to the heat exchange tube 500 and ensuring that the residual amount of isothermal medium in the heat exchange tube 500 remains constant when the pump is shut down, the problem of system heat capacity fluctuation during multiple continuous titrations is effectively solved. Specifically, after each heat exchange, the fluid passage in the heat exchange tube 500 is immediately cut off when the pump is shut down, keeping the amount of isothermal medium water remaining in the heat exchange tube 500 constant. Since this residual amount remains consistent throughout the experiment, the overall heat capacity of the calorimetric system remains stable, thereby avoiding baseline drift and measurement errors caused by changes in residual water volume. This ensures that regardless of the number of continuous titrations, the reaction system is in the exact same initial heat capacity state before each titration, making the heat data obtained from each titration strictly comparable, thus completing continuous titration and continuous measurement.

[0029] In some embodiments of this application, such as Figure 2As shown, the heat exchange unit includes a heat exchange tube 500 disposed within the reaction system and a peristaltic pump 400 connected to the heat exchange tube 500. The heat exchange tube 500 is specifically a spiral glass tube or a U-shaped glass tube, placed inside the reaction system to increase the contact area with the reaction system. The peristaltic pump 400 is connected to the heat exchange tube 500 via a silicone conduit 600, forming a circulation loop with the constant temperature environment (such as a constant temperature water bath). Specifically, the inlet of the peristaltic pump 400 is connected to the constant temperature environment via the silicone conduit 600, the outlet of the peristaltic pump 400 is connected to one end of the heat exchange tube 500 via the silicone conduit 600, and the other end of the heat exchange tube 500 returns to the constant temperature environment via the silicone conduit 600, thus forming a complete circulation loop. When the peristaltic pump 400 starts, it draws a constant temperature medium (e.g., water) from the constant temperature environment and drives the constant temperature medium to flow through the heat exchange tube 500 at a constant rate, achieving efficient heat exchange between the reaction system and the constant temperature environment.

[0030] When the peristaltic pump 400 is shut down, its hose is naturally compressed by the pump head, immediately cutting off the fluid passage within the heat exchange tube 500, preventing the isothermal medium within the heat exchange tube 500 from flowing back or continuing to flow. Since the peristaltic pump 400 is located at the outlet end of the circulation loop (i.e., the position where the isothermal medium enters the pump after flowing out of the heat exchange tube 500), when the peristaltic pump 400 is shut down, the isothermal medium within the heat exchange tube 500 is locked inside the pipe, maintaining a constant residual amount. Throughout the experiment, regardless of the number of consecutive titrations, the residual amount of isothermal medium in the heat exchange tube 500 remains consistent after each heat exchange, thus ensuring the overall heat capacity of the calorimetric system remains stable. This structural design allows the heat exchange unit to achieve active heat exchange while also possessing a liquid retention function, eliminating the need for additional solenoid valves or check valves, simplifying the system structure, and improving reliability.

[0031] The aforementioned reaction system refers to the material system consisting of the solution, reactants, products, and solvent contained within a calorimetric container. It is the core object for heat measurement and temperature control. To effectively isolate this material system from the external environment, it is typically placed in a calorimetric container with excellent thermal insulation, such as a Dewar 700 reaction vessel. The calorimetric container not only provides a stable physical boundary for the reaction system but also minimizes heat exchange with the external environment, thereby ensuring the accuracy of calorimetric measurements.

[0032] In some embodiments of this application, a constant temperature environment is provided by a constant temperature bath 800, which contains a constant temperature solution (e.g., water). A heater, a cooler, and a circulating stirring device are provided outside the bath to precisely control the temperature of the solution in the bath at a preset value (e.g., 25 ± 0.01 °C).

[0033] In some embodiments of this application, such as Figure 2As shown, the heat exchange controller includes a heat exchange unit, a temperature monitoring unit, and a control unit. The heat exchange unit, used for heat exchange with the reaction system, specifically includes a spiral or U-shaped glass micro heat exchange tube 500 disposed within the calorimetric container and a peristaltic pump 400 connected to the heat exchange tube 500. The peristaltic pump 400 is used to extract a constant-temperature medium from the constant-temperature environment and drive it to flow through the heat exchange tube 500.

[0034] The temperature monitoring unit is used to monitor the temperature of the reaction system in real time. The temperature monitoring unit includes a temperature sensor 300 installed inside the calorimetric container and a temperature acquisition module 200 electrically connected to it. The temperature acquisition module 200 can employ a high-precision analog-to-digital converter (ADC), such as an ADC consisting of a 24-bit ADC 270, a constant current source 230, a reference resistor 240, and a variable gain amplifier 250, to achieve accurate acquisition and conversion of the temperature signal. The temperature sensor 300 can be a TP1000 temperature sensor, or other types of resistance temperature detectors, such as a PT100 platinum resistance thermometer, or a thermocouple as the sensing element. Correspondingly, the temperature acquisition module 200 can be configured with a corresponding signal conditioning circuit according to the type of the selected temperature sensor 300, such as a cold junction compensation circuit for the thermocouple or a constant voltage excitation source for the thermistor, as long as the temperature value of the reaction system can be obtained accurately and in real time. The temperature acquisition module 200 is used to acquire and process the temperature signal and transmit the processed temperature data to the control unit.

[0035] The control unit is specifically the titration control system 100, which is electrically connected to the heat exchange unit and the temperature monitoring unit. The titration control system 100 can be a programmable logic controller, a microcontroller, or an industrial control computer, or other devices with logic operation and control instruction output functions. It has a preset control program to coordinate the titration operation and heat exchange control.

[0036] When the heat exchange controller provided in this embodiment is applied to titration calorimetry experiments, it first places the reaction system in a constant temperature environment to achieve thermal equilibrium between the temperature of the reaction system and the ambient temperature. The titration control system 100 continuously monitors the temperature of the reaction system through a temperature monitoring unit and repeats the following operations until the preset number of titrations is reached: Specifically, before each titration begins, the titration control system 100 first acquires the temperature baseline value of the reaction system through the temperature monitoring unit. This temperature baseline value is the temperature of the reaction system in thermal equilibrium before the titration operation. For example... Figure 3As shown, before each titration begins, the titration control system 100 first acquires the temperature baseline value of the reaction system through the temperature monitoring unit. This temperature baseline value is the temperature of the reaction system in thermal equilibrium before the titration operation. The line segment ab in the figure represents the baseline acquisition stage, during which the temperature of the reaction system remains constant. Once the temperature baseline value is acquired (reaching point b), the titration control system 100 issues a command to execute the titration operation and initiate the titration reaction. During the titration reaction stage (line segment bc), the titration control system 100 keeps the heat exchange unit closed, preventing active heat exchange with the reaction system and allowing the temperature of the reaction system to change naturally as the reaction progresses.

[0037] After the titration reaction is completed (point c), the titration control system 100 selects the optimal time (point d) to start the heat exchange unit according to preset conditions (such as the set sampling length or time) to perform heat exchange on the reaction system. Specifically, the titration control system 100 starts the peristaltic pump 400 to draw the isothermal medium from the isothermal environment and drives the isothermal medium to flow through the heat exchange tube 500 placed in the reaction system at a constant rate, realizing efficient heat exchange between the reaction system and the isothermal environment. During this period, the temperature monitoring unit monitors the temperature of the reaction system in real time (line segment cd). When the temperature monitoring unit detects that the temperature of the reaction system has returned to the temperature baseline value collected before titration (point a'), the titration control system 100 immediately controls the heat exchange unit to stop heat exchange.

[0038] After the above process is completed, the temperature monitoring unit automatically starts the baseline acquisition (a'b' line segment) for the next titration. After reaching point b', the titration operation is performed again, and this cycle is repeated. Figure 3 The diagram shows three titrations (three peaks), with points b, b', and b'' triggering the titrations respectively; points c, c', and c'' corresponding to the end of each reaction; points d, d', and d'' corresponding to the optimal timing for initiating heat exchange in each reaction; and points a', a'', and a''' corresponding to the temperature returning to the baseline value in each reaction. The specific control flow is as follows: Figure 4 As shown, in practical applications, the number of titrations can be set according to experimental requirements. Each titration repeats the above cycle until the preset termination condition is reached. Throughout the process, the temperature monitoring unit continuously records the temperature changes of the reaction system, ultimately obtaining a continuous temperature data sequence containing the temperature change curves of each titration.

[0039] After the heat exchange unit is shut down, the control unit automatically initiates baseline acquisition for the next titration when the temperature monitoring unit detects that the rate of temperature change in the reaction system is lower than a preset threshold. This ensures that the reaction system has reached sufficient thermal equilibrium before each titration. The preset threshold can be set according to the experimental accuracy requirements, for example, it can be set to ±0.001℃ / s.

[0040] In some embodiments of this application, such asFigure 2 As shown, the temperature acquisition module 200 in this embodiment adopts a high-precision multi-channel temperature acquisition scheme. Specifically, it is controlled by a microcontroller 210 and consists of a multi-channel analog switch 220, a constant current source 230, a reference resistor 240, a variable gain amplifier 250, a low dropout linear regulator 260, a 24-bit analog-to-digital converter 270, and an RS485 communication interface 280. Each device works in concert according to a preset timing sequence to complete the high-precision acquisition, conditioning, conversion, and remote data interaction of multiple temperature signals.

[0041] The low-dropout linear regulator 260 provides a stable, low-noise power supply voltage for the entire temperature acquisition module 200. Its input is connected to an external DC power supply, and its output is connected to a microcontroller 210, a multiplexer 220, a constant current source 230, a variable gain amplifier 250, a 24-bit analog-to-digital converter 270, and an RS485 communication interface 280, respectively, to provide stable operating voltage for each device and effectively suppress the interference of power supply ripple on the accuracy of analog signal acquisition.

[0042] The constant current source 230 outputs a high-precision, constant excitation current to provide a standard excitation for temperature-sensitive resistor sensors. In this embodiment, the temperature sensor 300 is a TP1000 platinum resistance thermometer. The constant current source 230 applies a constant current to it, converting temperature changes into resistance changes, thereby generating a voltage signal proportional to the temperature across the temperature sensor 300. The reference resistor 240 is connected in series with the temperature sensor 300, receiving the same constant current excitation current, and generating a high-precision reference voltage signal. This reference voltage is used for proportional calibration during subsequent analog-to-digital conversion, effectively compensating for measurement errors caused by minor drift of the constant current source 230 and line voltage drops.

[0043] The multiplexer 220, controlled by the microcontroller 210, sequentially selects multiple channels of the temperature sensors 300, enabling time-division multiplexing of multiple temperature signals by a single constant current source 230, variable gain amplifier 250, and 24-bit analog-to-digital converter 270. In this embodiment, multiple input terminals of the multiplexer 220 are connected to temperature sensors 300 located at different positions within the reaction system, its output terminal is connected to the variable gain amplifier 250, and its control terminal is connected to the general-purpose input / output interface of the microcontroller 210.

[0044] The variable gain amplifier 250 differentially amplifies the voltage signal from the temperature sensor 300 selected by the multiplex analog switch 220 and the voltage signal from the reference resistor 240. Its gain is dynamically configured by the microcontroller 210 according to the current temperature measurement range to adapt to the optimal input range of the 24-bit analog-to-digital converter 270, thereby improving the acquisition signal-to-noise ratio and resolution.

[0045] The 24-bit analog-to-digital converter 270 performs ultra-high precision analog-to-digital conversion on the amplified differential analog voltage signal output from the variable gain amplifier 250, converting the analog quantity into a digital quantity, and outputting the corresponding digital sampled values ​​of the temperature sensor 300 and the reference resistor 240. The 24-bit analog-to-digital converter 270 is connected to the microcontroller 210 through a serial peripheral interface, and the microcontroller 210 controls the sampling timing and reads the conversion results.

[0046] The microcontroller 210, as the control core of the temperature acquisition module 200, is responsible for channel selection of the multi-channel analog switch 220, gain configuration of the variable gain amplifier 250, sampling timing control of the 24-bit analog-to-digital converter 270, reading and processing of sampled data, execution of the temperature calibration algorithm, and data packaging and communication control. Specifically, the microcontroller 210 has a built-in temperature calibration program. By reading the digital voltage of the sensor and the digital voltage of the reference resistor 240, it calculates the real-time resistance value of the temperature sensor 300 using a proportional measurement algorithm. Then, combined with the pre-stored calibration table and calibration coefficients, it calculates the measured physical temperature value. For example, for a PT100 or TP1000 platinum resistance sensor, the microcontroller 210 calculates the real-time resistance value according to the formula Rt = (V_sensor / V_ref) × Rref, and then obtains the corresponding temperature value through table lookup or polynomial fitting.

[0047] The RS485 communication interface 280 enables long-distance, interference-resistant data transmission between the temperature acquisition module 200 and the host computer or main control system. The microcontroller 210 packages the calculated multi-channel temperature data according to a preset communication protocol and uploads it to the titration control system 100 via the RS485 communication interface 280. At the same time, it receives instructions from the titration control system 100 for acquisition frequency configuration, calibration parameter setting, etc., to realize closed-loop adjustment of the acquisition strategy.

[0048] When the temperature acquisition module 200 in this embodiment is working, the low-dropout linear regulator 260 first provides regulated power. After the microcontroller 210 starts, it initializes each interface, configures the gain register of the variable gain amplifier 250, and sets the channel switching timing of the multi-channel analog switch 220 and the sampling rate of the 24-bit analog-to-digital converter 270. Subsequently, the constant current source 230 outputs a constant excitation current, and the microcontroller 210 controls the multi-channel analog switch 220 to select the first temperature sensor 300. The current flows sequentially through the channel of the multi-channel analog switch 220, the temperature sensor 300, and the reference resistor 240, forming a complete excitation circuit. The resistance of the temperature sensor 300 changes with the measured temperature, generating a voltage signal V_sensor proportional to the temperature at its two ends. The reference resistor 240 generates a high-precision reference voltage V_ref. The two voltages are output differentially to the variable gain amplifier 250. A variable gain amplifier 250 differentially amplifies the V_sensor and V_ref signals. The microcontroller 210 dynamically adjusts the gain according to the temperature measurement range, matching the signal amplitude to the optimal input range of the 24-bit analog-to-digital converter 270. The 24-bit analog-to-digital converter 270 samples and converts the amplified differential signal, performs proportional calibration using V_ref, and outputs a high-resolution digital sample value. The microcontroller 210 reads the digital sample value, calculates the real-time resistance of the temperature sensor 300 using a built-in algorithm, and calculates the measured physical temperature value using a calibration table and calibration coefficients. After single-channel acquisition, the microcontroller 210 controls the multi-channel analog switch 220 to switch to the next temperature sensor 300, repeating the above process to achieve multi-channel temperature polling acquisition. Finally, the microcontroller 210 packages the multi-channel temperature data and uploads it to the titration control system 100 via the RS485 communication interface 280, while simultaneously receiving instructions from the host computer to adjust the acquisition strategy.

[0049] To better illustrate this embodiment, the calorimetric principle of this embodiment is described below: To overcome the technical limitation of traditional constant-temperature titration calorimetry devices that cannot perform continuous measurements, this embodiment proposes a "quasi-isothermal" calorimetric principle. The scientific meaning of quasi-isothermal is that after the titration reaction, the reaction system is rapidly restored to its initial baseline temperature through a heat exchange unit, ensuring that the system temperature before and after the reaction is essentially constant and approximately equal to the ambient temperature. Only small temperature deviations are allowed during titration. The "quasi-isothermal" calorimetric principle allows the quasi-isothermal titration calorimeter to inherit the advantages of the isothermal environment method in terms of simple structure and ease of manufacture, while also satisfying the advantages of continuous titration and continuous testing of the isothermal method.

[0050] Specifically, in one embodiment, the quasi-isothermal titration calorimeter of this embodiment is calibrated using a reaction system of tris(hydroxymethyl)aminomethane (THAM) and hydrochloric acid as an example. The experiment was conducted at a constant temperature of 298.15 K. First, 100.000 mL of a 0.08604 mol / L THAM solution was added to the Dewar reaction cell 700. After the system reached thermal equilibrium, 4.99973 mL of a 0.09986 mol / L hydrochloric acid solution was added dropwise at a constant rate by the titration system. Ten repeated titrations were performed using both intermittent and continuous testing modes. The titration heat, dilution heat, reaction heat, and molar enthalpy of reaction were recorded for each titration. The experimental results are shown in Table 1.

[0051] Table 1. Enthalpy data of the reaction between HCl and THAM at T=298.15 K a Titration heat, b Hydrochloric acid dilution heat, c Heat of reaction d Molar enthalpy of reaction. In Table 1, "No" indicates the titration sequence number, with 1 to 10 corresponding to 10 repeated experiments. "IMM" and "CMM" represent intermittent and continuous testing modes, respectively. The former is the testing mode that can only be used in traditional constant-temperature titration calorimetry devices, while the latter is a new testing mode proposed in this embodiment. The meanings of the data in each column are as follows: Titration heat (-Δ) t H) is the enthalpy change value directly measured during each titration, in joules (J); heat of dilution (-Δ) d H) is the heat of dilution of the hydrochloric acid solution due to the concentration change during titration, measured in joules (J). It needs to be subtracted from the heat of titration to obtain the net heat of reaction; the heat of reaction (-Δ) r H) represents the net enthalpy change of the reaction after deducting the heat of dilution, in joules (J); molar enthalpy of the reaction (-Δ) r H m The heat of reaction per mole of reactant is expressed in kilojoules per mole (kJ / mol) and is a standard quantity characterizing the thermodynamic properties of a reaction.

[0052] Figure 1 The temperature-time curve of the hydrochloric acid-THAM titration reaction, measured using intermittent testing mode, is shown. From Figure 1 As can be seen, since the reaction system needs to be allowed to slowly recover to the initial temperature through natural heat exchange after each titration, 10 titrations produced 10 independent temperature peaks. After each titration, a data file needs to be saved. Therefore, a total of 10 independent data files were saved for 10 titrations, and the data showed discrete and segmented characteristics.

[0053] Figure 5 The thermoelectric potential curves of the hydrochloric acid-THAM titration reaction, measured using continuous testing mode, are shown. Figure 5 As can be seen, during each titration reaction stage, the temperature of the reaction system is allowed to deviate moderately (manifested as the rising segment of each titration peak). After the titration reaction is completed, the heat exchange controller provided in this embodiment actively performs heat exchange, so that the temperature of the reaction system quickly returns to the temperature baseline before the reaction (manifested as the rapid temperature recovery segment after each titration peak). Since the temperature is accurately reset after each titration, the starting temperature of each titration is consistent. Therefore, 10 titrations form a continuous and complete temperature-time curve. All data are saved in a single file, and the data are continuous and comparable.

[0054] As shown in Table 1, the molar enthalpies of reaction measured in 10 experiments using the continuous testing mode were -47.857 kJ / mol, -47.880 kJ / mol, -47.735 kJ / mol, -47.208 kJ / mol, -46.768 kJ / mol, -47.200 kJ / mol, -47.459 kJ / mol, -47.425 kJ / mol, -47.024 kJ / mol, and -47.253 kJ / mol, with an average value of -47.38 kJ / mol and a standard deviation of ±0.36 kJ / mol, which is highly consistent with the reported molar enthalpy of THAM-hydrochloric acid of -47.45 kJ / mol in the literature. Meanwhile, the average value measured using the intermittent testing mode was -47.50 kJ / mol, with a standard deviation of ±0.23 kJ / mol, which also agrees with the literature value. Both test modes offer good accuracy, but the continuous test mode enables continuous titration and measurement, with all data stored in a single file (e.g., ...). Figure 5 As shown), the intermittent testing mode requires waiting for natural thermal equilibrium after each titration, and 10 titrations produce 10 independent data files (such as...). Figure 1 (As shown in the figure). Therefore, the quasi-isothermal calorimetry method proposed in this embodiment significantly improves experimental efficiency and data continuity while ensuring measurement accuracy, providing a more convenient and reliable testing method for thermodynamics research.

[0055] Additionally, embodiments of this application provide a titration calorimetric system, comprising: titration calorimetry apparatus; And a heat exchange controller as described above, wherein the heat exchange unit of the heat exchange controller is disposed within the reaction system of the titration calorimeter, and the temperature monitoring unit of the heat exchange controller is disposed within the reaction system.

[0056] The titration calorimetry system provided in this application embodiment can realize the various processes implemented in the above embodiments and achieve the same beneficial effects. To avoid repetition, it will not be described again here.

[0057] In some embodiments of this application, the titration calorimetry system includes an automatic titration calorimetry device in a constant temperature environment and the aforementioned heat exchange controller. The automatic titration calorimetry device in a constant temperature environment includes a constant temperature chamber, a calorimetric chamber disposed within the constant temperature chamber, and a reaction system disposed within the calorimetric chamber. The constant temperature chamber contains a constant temperature solution (such as water) to maintain the constant temperature environment of the calorimetric chamber. The calorimetric chamber is a Dewar reaction cell 700 with a vacuum jacket to isolate the external ambient temperature from the influence of the internal reaction system.

[0058] In addition, embodiments of this application provide a titration calorimetry method applied to the heat exchange controller described above, the method comprising: Step S100: Place the reaction system in a constant temperature environment; Step S200: Continuously monitor the temperature of the reaction system using a temperature monitoring unit, and repeat the following operations until the preset termination condition is reached to obtain a temperature data sequence: Step S300: Collect the temperature baseline value through the temperature monitoring unit. The temperature baseline value is the temperature value of the reaction system in thermal equilibrium state before the titration operation. Step S400: After the temperature baseline value is acquired, perform the titration operation to carry out the titration reaction; Step S500: After the titration reaction is completed, start the heat exchange unit to exchange heat in the reaction system; Step S600: When the temperature of the reaction system recovers to the threshold range based on the temperature baseline, that is, when the reaction system is in a "quasi-isothermal" state, control the heat exchange unit to stop heat exchange.

[0059] In some embodiments of this application, the heat exchange unit includes a heat exchange tube 500 and a pump, wherein the heat exchange tube 500 is placed in the reaction system and the pump is connected to the heat exchange tube 500. Step S500, "starting the heat exchange unit to exchange heat with the reaction system," includes: Step S510: Start the pump to extract the constant temperature medium from the constant temperature environment and drive the constant temperature medium to flow through the heat exchange tube 500 to exchange heat with the reaction system.

[0060] In some embodiments of this application, step S600, "controlling the heat exchange unit to stop heat exchange," includes: Step S610: Control the pump to shut down, so that the amount of constant temperature medium remaining in the heat exchange tube 500 remains constant.

[0061] The titration calorimetry method provided in this application can realize the various processes implemented in the above embodiments and achieve the same beneficial effects. To avoid repetition, it will not be described again here.

[0062] In addition, one embodiment of this application also discloses an electronic device 900, such as... Figure 6 As shown, it includes: At least one processor 910; At least one memory 920 is used to store at least one program; The titration calorimetry method described above is implemented when at least one program is executed by at least one processor 910.

[0063] The electronic device 900 provided in this application embodiment can implement the various processes implemented in the above method embodiments and achieve the same beneficial effects. To avoid repetition, it will not be described again here.

[0064] In addition, embodiments of this application provide a computer-readable storage medium storing a processor-executable program, which, when executed by a processor, is used to implement the titration calorimetry method as described above.

[0065] The computer-readable storage medium provided in this application embodiment can implement the various processes implemented in the above method embodiments and achieve the same beneficial effects. To avoid repetition, it will not be described again here.

[0066] It will be understood by those skilled in the art that all or some of the steps and systems in the methods disclosed above can be implemented as software, firmware, hardware, and suitable combinations thereof. Some or all of the physical components can be implemented as software executed by a processor, such as a central processing unit, digital signal processor, or microprocessor, or as hardware, or as an integrated circuit, such as an application-specific integrated circuit. Such software can be distributed on a computer-readable medium, which can include computer storage media (or non-transitory media) and communication media (or transient media). As is known to those skilled in the art, the term computer storage media includes volatile and non-volatile, removable and non-removable media implemented in any method or technology for storing information (such as computer-readable instructions, data structures, program modules, or other data). Computer storage media includes, but is not limited to, RAM, ROM, EEPROM, flash memory or other memory technologies, CD-ROM, digital versatile disc (DVD) or other optical disc storage, magnetic cartridges, magnetic tape, disk storage or other magnetic storage devices, or any other medium that can be used to store desired information and is accessible to a computer. Furthermore, as is known to those skilled in the art, communication media typically contain computer-readable instructions, data structures, program modules, or other data in modulated data signals such as carrier waves or other transmission mechanisms, and may include any information delivery medium.

[0067] The embodiments of this application have been described in detail above with reference to the accompanying drawings. However, this application is not limited to the above embodiments. Within the scope of knowledge possessed by those skilled in the art, various changes can be made without departing from the spirit of this application.

Claims

1. A heat exchange controller for titrating calorimetry, characterized in that, include: A heat exchange unit, wherein the heat exchange unit is used to exchange heat with the reaction system; A temperature monitoring unit, which is used to monitor the temperature of the reaction system in real time; A control unit, electrically connected to the heat exchange unit and the temperature monitoring unit, is used to continuously monitor the temperature of the reaction system through the temperature monitoring unit after the reaction system is placed in a constant temperature environment, and repeatedly perform the following operations until a preset termination condition is reached to obtain a temperature data sequence: The temperature baseline value is collected by the temperature monitoring unit. The temperature baseline value is the temperature value of the reaction system in thermal equilibrium state before the titration operation. After the temperature baseline value is acquired, a titration operation is performed to carry out the titration reaction; Upon completion of the titration reaction, the heat exchange unit is activated to exchange heat with the reaction system. When the temperature of the reaction system recovers to a threshold range based on the temperature baseline, the heat exchange unit is controlled to stop heat exchange.

2. The heat exchange controller according to claim 1, characterized in that, The heat exchange unit includes: A heat exchange tube, wherein the heat exchange tube is placed within the reaction system; A pump connected to the heat exchange tube is used to draw a constant temperature medium from the constant temperature environment and drive the constant temperature medium to flow through the heat exchange tube. When the pump is turned off, the residual amount of the constant temperature medium in the heat exchange tube remains constant.

3. The heat exchange controller according to claim 2, characterized in that, The pump is a peristaltic pump.

4. The heat exchange controller according to claim 2, characterized in that, The heat exchange tube is a spiral heat exchange tube or a U-shaped heat exchange tube.

5. A titration calorimetric system, characterized in that, include: titration calorimetry apparatus; And the heat exchange controller according to any one of claims 1 to 4, wherein the heat exchange unit of the heat exchange controller is disposed within the reaction system of the titration calorimeter, and the temperature monitoring unit of the heat exchange controller is disposed within the reaction system.

6. A titration calorimetric method, characterized in that, The method, applied to the heat exchange controller of claim 1, comprises: The reaction system was placed in a constant temperature environment; The temperature of the reaction system is continuously monitored by a temperature monitoring unit, and the following operation is repeated until the preset termination condition is reached to obtain a temperature data sequence: The temperature baseline value is collected by the temperature monitoring unit. The temperature baseline value is the temperature value of the reaction system in thermal equilibrium state before the titration operation. After the temperature baseline value is acquired, a titration operation is performed to carry out the titration reaction; Upon completion of the titration reaction, the heat exchange unit is activated to perform heat exchange on the reaction system. When the temperature of the reaction system recovers to a threshold range based on the temperature baseline, the heat exchange unit is controlled to stop heat exchange.

7. The titration calorimetry method according to claim 6, characterized in that, The heat exchange unit includes a heat exchange tube and a pump. The heat exchange tube is placed inside the reaction system, and the pump is connected to the heat exchange tube. The starting heat exchange unit performs heat exchange on the reaction system, including: The pump is started to draw the constant temperature medium from the constant temperature environment and drive the constant temperature medium to flow through the heat exchange tube to exchange heat with the reaction system.

8. The titration calorimetry method according to claim 7, characterized in that, The control of the heat exchange unit to stop heat exchange includes: The pump is shut down to keep the residual amount of the isothermal medium in the heat exchange tube constant.

9. An electronic device, characterized in that, include: At least one processor; At least one memory for storing at least one program; The titration calorimetry method as described in any one of claims 6 to 8 is implemented when at least one of the programs is executed by at least one of the processors.

10. A computer-readable storage medium, characterized in that, It stores a processor-executable program, which, when executed by the processor, is used to implement the titration calorimetry method as described in any one of claims 6 to 8.

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