WO2021007876A1 - 一种光谱-电位-温度多维滴定分析仪及其使用方法 - Google Patents

一种光谱-电位-温度多维滴定分析仪及其使用方法 Download PDF

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Publication number
WO2021007876A1
WO2021007876A1 PCT/CN2019/097096 CN2019097096W WO2021007876A1 WO 2021007876 A1 WO2021007876 A1 WO 2021007876A1 CN 2019097096 W CN2019097096 W CN 2019097096W WO 2021007876 A1 WO2021007876 A1 WO 2021007876A1
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Prior art keywords
titration
measurement
temperature
reagent
control device
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PCT/CN2019/097096
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English (en)
French (fr)
Inventor
王飞
邹明强
张昂
艾连峰
王海洋
李响
温昊松
崔宗岩
柳吉芹
王宇曦
席飞
刘芳
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王飞
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Priority to JP2019572718A priority Critical patent/JP7272970B2/ja
Priority to US16/726,150 priority patent/US11353470B2/en
Publication of WO2021007876A1 publication Critical patent/WO2021007876A1/zh

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
    • G01N21/79—Photometric titration
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N25/00—Investigating or analyzing materials by the use of thermal means
    • G01N25/20—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity
    • 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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/16—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using titration

Definitions

  • the invention belongs to the technical field of measurement, and specifically relates to the technical field of analytical chemistry, and more specifically to a spectrum-potential-temperature multidimensional titration analyzer and a titration method.
  • Potentiometric titration uses a measuring electrode inserted into the measured solution to form a galvanic cell with the measured substance.
  • the change in the measured potential is used to characterize the change in the structure of the substance in the reaction solution and mark the chemical reaction process.
  • the disadvantage is that there are problems of electrode passivation and diaphragm blockage.
  • temperature titration technology uses a temperature sensor to sense the temperature change in the titration solution system.
  • the sensing element of the temperature sensor usually uses a thermistor. When the temperature of the reaction system changes slightly, its resistance value changes, and it has a measuring resistance.
  • Spectral titration is a non-destructive measurement method that analyzes the visible light signal changes through the solution and analyzes the reaction process. It has the advantages of fast response, wide measurement range, simple operation, and accurate structure. The disadvantage is that it can only characterize the structure of the colored substance. Change, the logo shows a color chemical reaction.
  • the disadvantages are: 1) Due to the inconsistency of the measurement objects, the matrix and measurement conditions of each experiment are different in a separate experiment, so the data of each chemical reaction is also different, and the comparison is based on different experimental data. During the analysis, there will be errors in the chemical reaction information obtained; 2) The small sample size cannot meet the sample requirements of multiple separate experiments, and multiple separate experiments also increase the experimental steps, extend the experimental time, and affect the experimental process.
  • the purpose of the present invention is to solve the problems in the prior art and provide a spectrum-potentiometric-temperature multi-dimensional titration analyzer that can provide synchronous measurement results for the same chemical reaction process.
  • the analyzer can meet the simultaneous measurement requirements of different analysis methods in chemical analysis, improve the measurement accuracy between different measurement methods, effectively reduce the workload of multiple separate experiments, and can achieve simultaneous measurement for the same analysis object and different analysis methods .
  • a spectrum-potential-temperature multidimensional titration analyzer comprising a reagent control system, a titration measurement system, and a data processing system, the reagent control system being connected to the data processing system through the titration measurement system;
  • the reagent control system includes a reagent cabin and a measurement cabin, and the reagent cabin and the measurement cabin are connected through a reagent pipeline;
  • the titration measurement system includes a spectrum titration measurement device, a temperature titration measurement device, and a potentiometric titration measurement device, and the spectrum titration measurement device, the temperature titration measurement device and the potentiometric titration measurement device are arranged in parallel inside the measurement cabin;
  • the data processing system includes a measurement signal conversion and calculation device, and the measurement signal conversion and calculation device is respectively connected to the spectrometric titration measurement device, the temperature titration measurement device, and the potentiometric titration measurement device through signals.
  • At least one of the measurement chambers is in communication with at least one of the reagent chambers.
  • one of the measurement chambers is in communication with a plurality of reagent chambers; in other cases, more One of the measurement chambers is connected to one of the reagent chambers.
  • titration chemical analysis the change and measurement of the substance structure in the reaction solution is the basis of chemical analysis, while spectral titration, temperature titration, and potentiometric titration use different physical quantities to provide structural feature information for chemical reactions and changes in the substance structure.
  • the potentiometric titration method characterizes the progress of chemical reactions based on the changes in the electrochemical potential of substances with different structures in the reaction solution.
  • the structure of the substance participating in the chemical reaction in the reaction process changes, and the electrode potential Es of the structure changes continuously.
  • the electrode potential has a predetermined jump, it indicates that the titration has reached
  • different parameters and derivative parameters are used to identify and/or characterize the chemical reaction and the change in the structure of the substance and the change process.
  • enthalpy change ( ⁇ H)
  • T the temperature of the reaction system
  • ⁇ S the change in entropy. Therefore, as the temperature titration reaction occurs, heat is released into the environment or absorbed from the environment, and the temperature of the solution will rise or fall. At this time, the temperature can be used as a measurement parameter to identify and/or characterize the chemical reaction and its substances Structural changes and process of change.
  • potentiometric titration technology and temperature titration technology are mature chemical analysis measurement technologies.
  • the precision and accuracy of individual instrument measurement will not be reduced; as a new invention technology of the inventor, the spectrometric titration technology can verify the aforementioned mature technology in terms of its application, and in terms of data noise, data correction, measurement curve processing, etc. New applications have been obtained.
  • the present invention combines three technologies on the same instrument. Compared with the existing single technology and a single instrument, the reagent system and data processing device are shared in structure, which can significantly reduce the cost of the instrument; Synchronous comparison of measurement method data can obtain multi-dimensional measurement data for the same measurement target without relative error. Through comparison and analysis between different measurement technology data, it can provide different perspectives for the change process of material structure in chemical reactions. , The analysis results of different characterization parameters, improve the accuracy of different measurement methods and the accuracy of analysis methods, effectively reduce the workload of titration analysis, it is possible to obtain more accurate measurement methods and discover new physical properties and structural data of substances.
  • the invention adopts the multi-dimensional synchronous analysis technology of the same reaction process to provide a new analysis technology platform for analytical chemistry.
  • the reagent compartment includes a titration solution storage container, a reagent control device, and a first temperature control device.
  • the titration solution storage container is connected to the reagent control device through a reagent pipeline, and the first temperature control device is connected to the first temperature control device.
  • the reagent control device includes a protective gas component, a gas filter component, and a liquid sensing component, and the protective gas component provides a protective gas environment for the titration reagent in the titration liquid storage container, and the gas filter component is used to achieve air gas ,
  • the liquid sensing component senses the remaining amount of the titrant in the titrant storage container;
  • the first temperature control device includes a heating component, a temperature drop component and a temperature sensing component, and the first temperature control device provides a constant temperature environment for the titration reagent.
  • the protective gas assembly includes a protective gas pipeline and a valve
  • the at least one protective gas pipeline includes at least one protective gas inlet and at least one valve.
  • the gas filter assembly includes a purifier container, an air pipeline, a purified gas pipeline, and a plurality of valves. Air enters the purifier container through the air pipeline, and the air is removed by the purifier according to titration requirements.
  • the interfering substances in the gas such as carbon dioxide, oxygen or water, etc.
  • the filtered clean gas enters the titration liquid storage container through the purified gas pipeline; the air pipeline and the purified gas pipeline are equipped with valves to control the opening and closing of the gas circuit, Air velocity.
  • the liquid sensing component includes a magnetic sensor and a non-contact sensor; the magnetic sensor is arranged on the outer wall of the titration liquid storage container to sense the height of the titration liquid level in the titration liquid storage container; The non-contact sensor is arranged at the mouth of the titration solution storage container to sense the volume information of the solution in the titration solution storage container.
  • the storage temperature of the titration reagent is basically synchronized with the ambient temperature.
  • the ambient temperature changes, changes such as crystallization, precipitation, gas production, and volatilization may occur, causing the reagents The concentration and stability of the solution change, which affects the measurement result.
  • the present invention reduces the influence of the ambient temperature on the storage reagents by setting the first temperature control device in the reagent compartment, and keeps the storage reagents at the required high temperature or low temperature for constant temperature preservation according to the setting, and can also adjust the titration solution based on the needs of titration measurement. Pre-heating or cooling treatment is beneficial to the chemical titration.
  • the present invention adopts the setting of the protective gas component and the gas filter component of the reagent control device as the titration reagent Provide a protected environment of filtered clean gas and inert gas, so as to avoid the influence of reactive gas in the air on the titration reagent.
  • the titration solution storage container and the purifying agent container are respectively provided with a sealed container mouth to avoid material exchange between the titration solution and the purifying agent and the outside world, and to ensure the stability of the storage environment conditions of the titration solution and the purifying agent. .
  • the measurement chamber includes a mechanical arm, a titration head, a titration control device, a reaction vessel, a stirring device, a cleaning device, a second temperature control device, a gas protection device and a feedback signal device;
  • the titration head and the measurement bulkhead are connected by the mechanical arm to realize the relative displacement of the titration head and the reaction vessel;
  • the titration control device, the stirring device, the cleaning device, and the gas protection device are respectively connected to the titration head, and the relative displacement with the reaction container is realized through the titration head;
  • the feedback signal device is respectively connected with the mechanical arm, the titration control device, the stirring device, the cleaning device, the second temperature control device, and the gas protection device through signals, and the second temperature control device is used to control the titration reaction
  • the temperature of the container, the gas protection device is used to provide a protective gas environment for the titration reaction;
  • the titration control device is connected with the reagent control device through a pipeline, and the feedback signal device is signally connected with the measurement signal conversion and calculation device.
  • a solution overflow hole is provided on the side wall of the reaction vessel to ensure that the reaction solution in the reaction vessel will not overflow from the upper edge of the reaction vessel, and a waste liquid collection tray is also provided on the outside of the reaction vessel ,
  • the waste liquid collecting tray includes a waste liquid outlet, and the overflowing solution is discharged from the measurement chamber through the waste liquid outlet.
  • the cleaning device includes a cleaning fluid component and a cleaning gas component, and the cleaning fluid component rinses the stirring device immersed in the reaction solution by spraying the cleaning fluid, the light signal sensor, the temperature signal sensor, and the potential signal sensor.
  • the cleaning gas assembly is flushed with clean air or inert gas to wash the stirring device, the light signal sensor, the temperature signal sensor and the potential signal sensor immersed in the reaction solution.
  • the titration control device includes at least one reagent adding component and a liquid surface distance sensor.
  • the speed, type, and time of adding the titration reagent are controlled by the opening and closing of the reagent adding component, and the liquid surface distance sensor is Control the distance between the titration head and the reaction vessel.
  • the present invention realizes the relative displacement of the titration control device, stirring device, cleaning device and gas protection device with the reaction vessel through the integrated setting of the mechanical arm and the titration head. It avoids frequent manual operations when using existing instruments, thereby increasing the analysis speed and reducing the workload of the analysts.
  • the present invention adjusts the adding speed, the type of reagent or the time point of adding the titration reagent through the titration control device in the measuring chamber; the setting of the stirring device ensures the uniformity of the reaction solution system, thereby realizing the accuracy of the titration measurement; Moreover, in consideration of the automation of the multidimensional titrator and the continuity of titration measurement, the present invention avoids cross contamination of the reaction solution during continuous multiple measurements by connecting the cleaning device with the pipeline of the reaction vessel and the stirring device. Continuous measurement creates conditions for measurement quality assurance.
  • the reaction temperature and reaction atmosphere have an important influence on the titration reaction measurement.
  • the sample needs to be titrated in the boiling state.
  • the reaction environment at room temperature can no longer meet the requirements of the determination conditions; for example, in the determination of the peroxide value of fats, oxygen in the air can oxidize the fats. Affect the determination of peroxide value.
  • the presence of an inert atmosphere has an important impact on the accuracy of the reaction measurement result.
  • the present invention ensures that the titration reaction environment can be adjusted according to different titration reactions, thereby ensuring the wide applicability of the multidimensional titrator and the accuracy of the reaction measurement results.
  • the temperature titration measurement device includes a temperature signal sensor
  • the potentiometric titration measurement device includes a potential signal sensor
  • the spectrometric titration measurement device includes a light signal sensor, and the temperature signal sensor, the potential signal sensor, and the light The signal sensor is connected to the reaction vessel through a signal;
  • the temperature signal sensor and the potential signal sensor are connected with the titration head, and the relative displacement with the reaction container is realized through the titration head;
  • the spectrometric titration measurement device further includes a light source and a light signal loading component, and the light source, the light signal loading component, and the light signal sensor are sequentially connected through the light signal.
  • the light source is an uninterrupted continuous light source with an emission wavelength of 380 nm to 780 nm, and optical signals of one, several or all wavelengths emitted by the light source are directed toward the chemical reaction solution through the optical signal loading component, After being absorbed and/or reflected by the chemical reaction solution, the optical signal sensor provides spectral measurement information to the measurement signal conversion and calculation device.
  • the temperature signal sensor, the potential signal sensor, and the light signal sensor can independently or synchronously detect the titration reaction in the reaction vessel.
  • the measurement data of each measurement point can be regarded as the measurement data of the same reaction system at the same time and different measurement modes.
  • the measurement data of different measurement points of the same measurement mode or the measurement data of different measurement modes of the same measurement point can be compared and analyzed, and the material structure characterization information of different physical and chemical parameters based on the same measurement conditions can be obtained, thereby realizing the reaction solution Characterization and metrological analysis of changes in the structure of substances in China.
  • the optical signal loading component includes an optical lens, and the optical lens is disposed on the outer wall of the reaction vessel.
  • the one optical lens is on one outer wall of the reaction vessel; in another case, the two optical lenses Are arranged in parallel on the outer wall of the reaction vessel, and the first optical lens is on one outer wall of the reaction vessel, the second optical lens is on the outer wall of the opposite side of the reaction vessel, the light source, The first optical lens and the second optical lens are sequentially on a straight line.
  • the optical signal loading component further includes a reflector, and the reflector is arranged on the outer wall or inside of the reaction vessel.
  • the reflector is located inside the reaction vessel, and the measurement light emitted by the light source is directed toward the reaction solution through the optical lens on the outer wall of the reaction vessel, and then is reflected by the reflector inside the reaction solution before passing through
  • the optical lens is directed toward the optical signal sensor, and the light source, the optical lens, and the reflector are sequentially on a straight line;
  • the reflector is located on the outer wall of the reaction vessel, and the measuring light emitted by the light source is directed toward the reaction solution through the first optical lens on the outer wall of the reaction vessel, and then passes through the outer wall of the reaction vessel.
  • the second optical lens is directed toward the reflector located on the outer wall of the reaction vessel, and after reflection, it passes through the reaction solution and is directed toward the optical signal sensor through the first optical lens.
  • the light source, the first optical lens, the second optical lens and the reflector The mirrors are in a straight line in sequence.
  • the spectrum-potential-temperature multi-dimensional titration analyzer for chemical reactions further includes a data output display system connected to the data processing system to realize the synchronous output and display of multi-dimensional titration parameters.
  • Another object of the present invention is to provide a method for using the spectrum-potential-temperature multidimensional titration analyzer.
  • a titration method of a spectrum-potential-temperature multi-dimensional titration analyzer includes the following steps:
  • Set measurement parameters set at least one measurement parameter in the data processing system, select one or more of the spectrum titration mode, temperature titration mode, and potentiometric titration mode, and select at least one measurement parameter in the titration mode ;
  • the titration reagent in the titration storage container is added to the reaction container through the reagent control device and the titration control device, and reacts with the titrated solution obtained in step S4, using the spectral titration measuring device, temperature titration measuring device, One or more of the potentiometric titration measurement devices simultaneously measure the reaction solution in the reaction vessel, and obtain measurement data corresponding to the measurement parameters and measurement parameters set in step S5;
  • step S7 Use the data processing system to store and analyze the measurement data obtained in step S6, and use the data output display system to synchronously display the measurement data;
  • the feedback signal device terminates the operation of the titration control device, gas protection device, stirring device and the second temperature control device, and turns on the cleaning device to clean the stirring device, light signal sensor and temperature signal immersed in the reaction solution Sensors, potential signal sensors.
  • the titration parameters of the titration reagent described in step S3 include one or more of the titration rate, titration time, and titration type of the titration reagent.
  • the measurement parameters described in step S5 include time t and its derivative parameters, pulse signal f and its derivative parameters, pH value of the reaction solution and its derivative parameters, added reagent volume V and its derivative parameters, reaction solution One or more of the substance concentration C and its derivative parameters, the potentiometric titration parameter Es and its derivative parameters, the temperature titration parameter T and its derivative parameters, and the spectral titration parameter S and its derivative parameters.
  • the measurement parameter is the measurement standard selected for the purpose of clarifying the measurement point and constructing the titration curve.
  • the time t or the reagent volume V is often selected as the measurement standard.
  • the measurement parameters of the present invention include the potentiometric titration parameter Es and its One or more of the derivative parameters, the temperature titration parameter T and its derivative parameters in the temperature titration mode, and the spectral titration parameter S and its derivative parameters in the spectral titration mode.
  • the derivative parameter is at least one measurement parameter or at least one measurement parameter set as an independent variable parameter, and any dependent variable parameter is obtained through at least one calculation by a calculation method known in the art. It should be understood that all other measurement parameters or derivative parameters of measurement parameters obtained by those of ordinary skill in the art without creative work fall within the protection scope of the present invention.
  • the measurement mode of the spectral titration mode in step S5 includes a total transmission mode, a total transmission-total reflection mode, a semi-transmission-semi-reflection mode or a reflection mode.
  • the total transmission mode is a non-contact measurement method.
  • the light from the light source enters the reaction vessel from the side of the reaction vessel equipped with the first optical lens, and part of the wavelength light of the light source is absorbed in the reaction solution.
  • the signal light with the absorption signal is emitted from the opposite side of the reaction container through the second optical lens and out of the reaction container, and the spectral information is led to the measurement signal conversion and calculation device through the optical signal sensor to obtain the absorption information of the reaction solution;
  • the total transmission-total reflection mode is a non-contact measurement method.
  • the light from the light source enters the reaction vessel from the side of the reaction vessel equipped with the first optical lens. Part of the wavelength light of the light source is absorbed in the reaction solution, and the absorption signal is loaded.
  • the reflector set on the outer wall of the reaction vessel reflects the signal light into the reaction solution again, is absorbed again and loads the absorption signal, and then from the first optical
  • the lens shoots out of the reaction vessel, and the optical signal sensor introduces the spectral information into the measurement signal conversion and calculation device to obtain the absorption information of the reaction solution.
  • the one-time measurement process of the total transmission-total reflection mode includes two processes of loading the absorption signal to achieve an increase in signal strength;
  • the semi-transmission-semi-reflective mode belongs to the contact measurement mode.
  • the light from the light source enters the reaction solution from the optical lens, and part of the wavelength light of the light source is absorbed in the reaction solution.
  • the signal light loaded with the absorption signal is reflected by the mirror inside the solution.
  • the light-returning lens emits out of the reaction container, and the spectral information is imported into the measurement signal conversion and calculation device through the optical signal sensor to obtain the absorption information of the reaction solution;
  • Reflective mode is a non-contact measurement method.
  • the light from the light source enters the reaction solution from the optical lens, and part of the wavelength light of the light source is absorbed by the surface of the reaction solution.
  • the signal light loaded with the absorption signal is reflected out of the reaction vessel on the surface of the solution and passes through the light.
  • the signal sensor introduces the spectral information into the measurement signal conversion and calculation device to obtain the absorption information of the reaction solution.
  • the measurement method of the temperature titration mode in step S5 includes an immersion contact type, a wall contact type, a solution surface irradiation type or a container surface irradiation type.
  • the immersion contact type is to immerse the sensor in the reaction solution, and the temperature change of the reaction solution is directly transmitted to the temperature sensor;
  • the wall-to-wall contact type is a contact measurement, in which the temperature sensor is closely attached to the outer wall of the reaction vessel, and after the temperature change of the reaction solution is transmitted to the reaction vessel, it is then transmitted to the temperature sensor through the reaction vessel;
  • the solution surface irradiation type is a non-contact measurement, which focuses the infrared energy signal radiated from the surface of the reaction solution on a temperature sensor and converts it into a corresponding electrical signal;
  • the container surface irradiation type is a non-contact measurement, which transfers the heat change of the reaction solution to the surface of the reaction container, and the infrared energy signal radiated from the surface of the reaction container is focused on the temperature sensor and converted into a corresponding electrical signal.
  • the working principle of the present invention is: in the same determination process, the spectrometric titration measuring device, the potentiometric titration measuring device and the temperature measuring device are connected in parallel, and the measurement parameters are measured simultaneously or individually to obtain the spectral titration parameters under the same chemical reaction conditions. Potentiometric titration parameters and temperature measurement parameters greatly reduce or even eliminate the error between measurement parameters in different measurement modes caused by different measurement conditions, reduce the workload of multiple titrations of the same sample, and have high measurement accuracy; and use the reagent compartment With the setting of the measuring chamber, the environmental conditions are uniformly measured, and the external interference is small, which improves the sensitivity and accuracy of the multidimensional titration and makes the measurement results more accurate and reliable.
  • the titration environment conditions are unified, the external interference is reduced, and the signal-to-noise ratio of the titration system is improved, and the detection sensitivity of multidimensional titration is improved;
  • the unit has clear functions, simple structure, easy integration and miniaturization, and can realize semi-automatic and batch detection of titration reaction;
  • Fig. 1 is a schematic diagram of a spectrum-potential-temperature multi-dimensional titration analyzer provided by the present invention.
  • Figure 2 is a schematic diagram of the reagent compartment of a spectrum-potential-temperature multidimensional titration analyzer provided by the present invention.
  • FIG. 3 is a schematic diagram of a reagent control device in a reagent compartment of a spectrum-potential-temperature multidimensional titration analyzer provided by the present invention.
  • FIG. 4 is a schematic diagram of the protective gas component and the liquid sensing component of the reagent control device in the reagent compartment of the spectrum-potential-temperature multidimensional titration analyzer provided by the present invention.
  • FIG. 5 is a schematic diagram of the gas filter assembly of the reagent control device in the reagent compartment of the spectrum-potential-temperature multidimensional titration analyzer provided by the present invention.
  • Fig. 6 is a schematic diagram of a measurement chamber of a spectrum-potential-temperature multidimensional titration analyzer provided by the present invention.
  • Fig. 7 is a schematic diagram of a measuring chamber titration head of a spectrum-potential-temperature multi-dimensional titration analyzer provided by the present invention.
  • FIG. 8 is a schematic diagram of the optical paths of the four measurement modes of the spectrum titration mode of a spectrum-potential-temperature multi-dimensional titration analyzer provided by the present invention.
  • Figure 9 is a multi-dimensional titration curve provided by Experimental Example 1 of the present invention.
  • Figure 10 is the potential (A), spectrum (B), and temperature (C) titration curves provided by Experimental Example 2 of the present invention.
  • a multidimensional titrator includes a reagent control system, a titration measurement system, and a data processing system.
  • the reagent control system is connected to the data processing system through the titration measurement system.
  • the reagent control system includes a reagent cabin 1 and a measurement cabin 2, and the reagent cabin 1 and the measurement cabin 2 are connected through a pipeline 8.
  • the reagent compartment 1 includes a titration solution storage container 101, a reagent control device 102, and a first temperature control device 103.
  • the titration solution storage container 101 and the reagent control device 102 are connected through a reagent pipeline, and the first temperature control device 103 is connected to the titration solution.
  • Liquid storage container 101 is connected;
  • the reagent control device 102 includes a protective gas component 1021, a gas filter component 1022, and a liquid sensing component 1023, and the protective gas component 1021 provides a protective gas environment for the titration reagent in the titration solution storage container 101, and the gas filter component 1022 is used to To realize the filtration of air and gas, the liquid sensing component 1023 senses the remaining amount of the titrant in the titrant storage container 101;
  • the protective gas assembly 1021 includes a protective gas pipeline 10211 and a valve 10212, and at least one protective gas pipeline 10211 includes at least one protective gas inlet 10213 and at least one valve 10212.
  • the gas filter assembly 1022 includes a purifying agent container 10221, an air pipe 10222, a purified gas pipe 10223, and a plurality of valves 10224.
  • the air enters the purifying agent container 10221 through the air pipe 10222, and the air is removed by the purifier according to titration requirements.
  • the carbon dioxide, oxygen or water in the air, the filtered clean gas enters the titration liquid storage container 101 through the purified gas pipeline 10223; the air pipeline 10222 and the purified gas pipeline 10223 are equipped with valves 10224 to regulate the opening and closing of the gas circuit and the air flow speed;
  • the liquid sensing component 1023 includes a magnetic sensor 10231 and a non-contact sensor 10232.
  • the magnetic sensor 10231 is arranged on the outer wall of the titration liquid storage container 101 to sense the height of the titration liquid in the titration liquid storage container 101; the non-contact sensor 10232 Set at the mouth of the titration solution storage container 101 to sense the air pressure in the titration solution storage container 101;
  • the first temperature control device 103 includes a heating component, a temperature drop component and a temperature sensing component, and the first temperature control device 103 provides a constant temperature environment for the titration reagent.
  • the measurement chamber 2 includes a robotic arm 201, a titration head 202, a titration control device 203, a reaction vessel 204, a stirring device 205, a cleaning device 206, a second temperature control device 207, a gas protection device 208, and a feedback signal device 209;
  • the titration head 202 is connected to the measurement bulkhead through the robotic arm 201, the titration control device 203, the stirring device 205, the cleaning device 206, and the gas protection device 208 are respectively connected to the titration head 202, and the feedback signal device 209 is respectively connected to the robotic arm 201 and the titration control device 203.
  • the stirring device 205, the cleaning device 206, the second temperature control device 207, and the gas protection device 208 are connected by signals;
  • the titration control device 203 and the reagent control device 102 are in communication through the pipeline 8;
  • the side wall of the reaction vessel 204 is also provided with a solution overflow hole 2041 to ensure that the reaction solution in the reaction vessel 204 will not overflow, and a waste liquid collection tray 2042 is also provided on the outside of the reaction vessel 204 to collect the overflow from the solution.
  • the solution overflowing in the flow hole 2041, the waste liquid collecting tray 2042 includes a waste liquid outlet 2043, and the overflowing solution is discharged from the measurement chamber 2 through the waste liquid outlet 2043;
  • the cleaning device 206 includes a cleaning liquid component 2061 and a cleaning gas component 2062.
  • the cleaning liquid component 2061 rinses the stirring device 205 immersed in the reaction solution by spraying the cleaning liquid, the light signal sensor 504, the temperature signal sensor 6 and the potential signal sensor.
  • the cleaning gas assembly 2062 uses clean air or inert gas to purge the stirring device 205, the light signal sensor 504, the temperature signal sensor 6 and the potential signal sensor 7 immersed in the reaction solution with clean air or inert gas;
  • the titration control device 203 includes at least one reagent adding component 2031 and a liquid surface distance sensor 2032.
  • the reagent adding component 2031 can be opened and closed to control the speed, type and adding time of the titration reagent.
  • the liquid surface distance sensor 2032 can control the titration head 202. The distance from the reaction vessel 204.
  • the titration measurement system includes a spectrum titration measurement device 5, a temperature titration measurement device, and a potentiometric titration measurement device, and the spectrum titration measurement device 5, the temperature titration measurement device and the potentiometric titration measurement device are arranged in parallel in the measurement cabin 2 Internal;
  • the spectrometric titration measurement device 5 includes a light signal sensor 504
  • the temperature titration measurement device includes a temperature signal sensor 6
  • the potentiometric titration measurement device includes a potential signal sensor 7, and the temperature signal sensor 6, the potential signal sensor 7,
  • the light signal sensor 504 and the reaction vessel 204 are connected by signals.
  • the spectrometric titration measurement device 5 further includes a light source 501 and a light signal loading component.
  • the light source 501, the light signal loading component, and the light signal sensor 504 are sequentially connected by optical signals;
  • the optical signal loading component includes a first optical lens 502, which is disposed on the outer wall of the reaction vessel 204; the optical signal loading component further includes a second optical lens 503, which is disposed on the reaction vessel 204.
  • the optical signal loading component further includes a reflecting mirror 505 which is arranged on the outer wall or inside of the reaction vessel 204.
  • the data processing system includes a measurement signal conversion and calculation device 3, and the measurement signal conversion and calculation device 3 is respectively connected with the spectrum titration measurement device 5, the temperature titration measurement device 6, and the potentiometric titration measurement device 7 through signals.
  • the spectrum-potential-temperature multi-dimensional titration analyzer for chemical reactions also includes a data output display system 4, which is connected to the data processing system to realize the synchronous output and display of multi-dimensional titration parameters.
  • the instrument When working, turn on the instrument to determine the remaining amount of reagents in the titrant storage container 101 and the cleaning agent container 10221, adjust the opening and closing of the valve 10212 or the valve 10224 to adjust the gas path and air flow speed, and let the air enter the gas filter assembly 1022 to remove Carbon dioxide, oxygen or water in the air, or the introduction of inert gas provides a protective gas environment for the titration reagent.
  • the first temperature control device 103 is turned on to store the titration reagent at a constant temperature.
  • the titrated liquid is added to the reaction vessel 204, and the mechanical arm 201 is adjusted to make the titration head 202 and the reaction vessel 204 reach an appropriate relative position.
  • the second temperature control device 207 and the gas protection device 208 are turned on to adjust the environmental parameters of the measurement chamber 2 and the reagent adding component 2031 controls the adding speed, type and adding time of the titration reagent.
  • the titration head 202 moves down to the mouth of the reaction vessel 204 and close it.
  • the titration reagent is added dropwise to the reaction vessel 204 from the titration solution storage container 101 via the reagent adding assembly 2031 through the pipeline 8, and the stirring device 205 is turned on.
  • the stirring device 205 is turned on.
  • the light signal sensor 504 the temperature signal sensor 6, and the potential signal sensor 7 for measurement.
  • the spectral titration measurement device 5 measures the titration reaction in the reaction vessel 204, wherein the total transmission mode (as shown in FIG. 8A) is that the light signal is emitted from the light source 501 and enters the reaction vessel through the first optical lens 502 204. After part of the wavelength light of the optical signal is absorbed in the reaction solution, the optical signal loaded with the absorption signal is emitted through the second optical lens 503, and the spectral information is imported into the measurement signal conversion and calculation device 3 through the optical signal sensor 504 to obtain Spectral measurement information of titration reaction;
  • the reflection mode (as shown in Figure 8B) is that the light signal is sent from the light source 501 directly into the reaction vessel 204, part of the wavelength light of the light signal is absorbed by the surface of the reaction solution, and the light signal loaded with the absorption signal is reflected by the surface of the solution and passes through the light signal sensor 504 Import the spectrum information into the measurement signal conversion and calculation device 3 to obtain the spectrum measurement information of the titration reaction;
  • the semi-transmission-semi-reflective mode (as shown in Figure 8C) is that the optical signal is emitted from the light source 501 and enters the reaction vessel 204 through the first optical lens 502. After part of the wavelength light of the optical signal is absorbed in the reaction solution, the absorption signal is loaded The optical signal is emitted by the reflection mirror 505 inside the solution, and then exits the reaction vessel 204 through the first optical lens 502, and the spectral information is imported into the measurement signal conversion and calculation device 3 through the optical signal sensor 504 to obtain the spectral measurement information of the titration reaction;
  • the total transmission-total reflection mode (as shown in Figure 8D) is that the optical signal is emitted from the light source 501 and enters the reaction vessel 204 through the first optical lens 502. After part of the wavelength light of the optical signal is absorbed in the reaction solution, the absorption signal is loaded The light signal is emitted through the second optical lens 503 and reflected by the mirror 505 again into the reaction solution. After being absorbed and loaded with the absorption signal again, it is emitted from the first optical lens 502 out of the reaction vessel 204, and the light signal sensor 504 The spectrum information is imported into the measurement signal conversion and calculation device 3 to obtain the spectrum measurement information of the titration reaction.
  • the measurement signal conversion and calculation device 3 sends a signal to the feedback signal device 209, the stirring device 205, the second temperature control device 207, the gas protection device 208, and the reagent adding assembly 2031 stop working, and the robotic arm 201 drives the titration head 202 to move Under the signal feedback of the liquid level distance sensor 2032, away from the reaction vessel 204, the cleaning device 206 starts to clean the stirring device 205, the light signal sensor 504, the temperature signal sensor 6, and the potential signal sensor 7, etc., which are immersed in the reaction solution, and pass the solution
  • the overflow hole 2041 discharges the reaction solution in the reaction vessel 204 through the waste liquid outlet 2043 of the waste liquid collecting tray 2042 out of the measurement chamber 2 for the next titration reaction to proceed.
  • a titration method of a spectrum-potential-temperature multi-dimensional titration analyzer the steps include:
  • Pre-treatment before measurement use a blank standard sample to calibrate the instrument reference, and after the calibration is completed, prepare the titrated solution in the reaction vessel 204 for standby;
  • the titration reagent in the titration solution storage container 101 is added to the reaction container 204 through the reagent control device and the titration control device 201, and reacts with the titrated solution obtained in step S4, and the reaction is measured by the spectral titration measurement device 5
  • the spectrum signal of the reaction solution in the container 204 obtains measurement data corresponding to the time t and the value of the measurement parameter L * set in step S5;
  • step S7 Use the data processing system to store and analyze the measurement data obtained in step S6, and use the data output display system 4 to synchronously display the measurement data;
  • the feedback signal device 206 terminates the operations of the titration control device 201, the gas protection device 202, the stirring device 203, and the second temperature control device 205, and turns on the cleaning device to clean the reaction vessel 204 and the stirring device 203.
  • a titration method of a spectrum-potentiometric-temperature multi-dimensional titration analyzer the steps are as described in Example 2, the difference is:
  • a titration method of a spectrum-potentiometric-temperature multi-dimensional titration analyzer the steps are as described in Example 2, the difference is:
  • the solution is transferred to the reaction vessel 204, and the solution is the sample solution to be tested.
  • the second temperature control device 207 is closed, the gas protection device 208 is activated, and the reaction vessel 204 is filled with water as a blank sample for measurement; the parts immersed in the liquid surface are cleaned and used for standby.
  • Set general parameters set the measurement period to 0.2s, the minimum volume of reagents added is 10 ⁇ L, the maximum volume of dripping 100 ⁇ L, and the stirring speed is 200 rpm.
  • Set measurement parameters start the tungsten light source and stabilize until the luminous flux is stable, select the full transmission measurement mode, spectral range 380nm ⁇ 780nm, interval 5nm, integration time ⁇ 2, slit width ⁇ 5.0, adjust the blank value of the device with water, measure Data acquisition spectral transmittance; select acid-base titration mode, pH electrode, and measure data acquisition potentiometric titration parameter Es; select contact invasive mode, temperature electrode, and measure data acquisition temperature titration parameter T.
  • the sodium standard solution is blank test volume number V white ;
  • the reagent temperature during measurement is 25°C
  • the volume of V white reagent consumed by the experimental blank is 0.05ml
  • the titration data is shown in Table 1.
  • the titration curve drawn with the titration volume as the abscissa and the measurement parameter as the ordinate is shown in Figure 9.
  • the volume of the unknown concentration of sodium hydroxide standard solution corresponding to the peak of the potentiometric titration end point is 32.85ml
  • the end point of the spectrum titration The volume of the sodium hydroxide standard solution of unknown concentration corresponding to the peak value is 32.80ml
  • the volume of the sodium hydroxide standard solution of unknown concentration corresponding to the temperature end point peak is 32.90ml.
  • the standard deviation (S) of a spectrum-potentiometric-temperature multi-dimensional titration analyzer is 0.0002, and the relative standard deviation (RSD%) is 0.18%.
  • the working standard reagent potassium hydrogen phthalate is dried to constant weight in an electric oven at 105°C ⁇ 110°C. Weigh 0.755g, 0.7587g and 0.7516g of potassium hydrogen phthalate on a balance with an accuracy of more than 0.1mg.
  • 80 mL of carbon dioxide-free water was used to dissolve potassium hydrogen phthalate solution.
  • the sodium standard solution is blank test volume number V white ;
  • test sample Volume number V The standard sodium hydroxide solution of unknown concentration consumed to reach the end of the titration is the test sample Volume number V.
  • the reagent temperature during the measurement is 25°C
  • the volume of V white reagent consumed by the experimental blank is 0.05 ml
  • the titration data is shown in Table 2.
  • the titration curve drawn with the titration volume as the abscissa and the measurement parameter as the ordinate is shown in Figure 10, where A is the potentiometric titration curve, B is the spectral titration curve, and C is the temperature titration curve.
  • the volume of the standard solution of sodium hydroxide of unknown concentration corresponding to the peak of the potentiometric titration end point is 32.95ml
  • the volume of the standard solution of sodium hydroxide of unknown concentration corresponding to the peak of the spectral titration end point is 32.75ml
  • the volume of the unknown concentration corresponding to the end peak of the temperature end point is 32.75ml.
  • the present invention changes a single titration measuring instrument to a multi-dimensional titrator with a spectrum titration measuring device, a potentiometric titration measuring device and a temperature measuring device in parallel, without changing the basis of the existing operating procedures
  • the error between the measurement parameters of different measurement modes caused by the different measurement conditions and the unknown chemical reaction process in the titration detection process can be corrected in real time by the measurement parameters of the unified measurement point, and the standard deviation of the three titration methods (S) is reduced from 0.0006 to 0.0002, and the relative standard deviation (RSD%) is reduced from 0.54% to 0.18%.
  • the present invention can realize simultaneous determination of multiple titration modes of the same sample, improve the analysis speed, reduce the analysis steps, and greatly reduce the workload of the analyst.

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Abstract

一种光谱-电位-温度多维滴定分析仪，包括并联设置的光谱滴定测量装置(5)、温度滴定测量装置(6)和电位滴定测量装置(7)，可以满足化学分析中不同分析方法的同步测量要求，提高了不同测量方法之间的测量精度，有效减少了多次单独实验的工作量，可以实现针对同一分析对象、不同分析方法的同步测量。光谱-电位-温度多维滴定分析仪的使用方法，通过对不同测量技术得到的数据之间进行比较分析，可以为化学反应中物质结构的变化过程提供不同的角度、不同表征参数的分析结果，衡量不同测量方法之间的精度和分析方法的正确度，有效减少滴定分析的工作量，并获得更准确的测量方法、发现新的物质物理特性和结构数据。

Description

一种光谱-电位-温度多维滴定分析仪及其使用方法 技术领域
本发明属于测量技术领域，具体涉及分析化学技术领域，更具体地涉及一种光谱-电位-温度多维滴定分析仪及滴定方法。
背景技术
滴定化学分析中，反应溶液中物质结构的变化与计量是化学分析中极其重要的基础工作。采用不同的测量方法针对相同的测定目标得到不同的测量数据，并通过数据之间的比较，可以为化学反应中物质结构的变化过程提供不同物理量的分析，是化学分析中应用广泛而及其重要的环节。
电位滴定是采用测量电极插入被测定溶液中，与被测量物质形成原电池，通过测量电势的变化表征反应溶液中物质结构变化、标识化学反应进程，缺点是存在电极钝化、隔膜堵塞的问题。温度滴定技术作为一种分析检测方法，采用温度传感器感应滴定溶液体系中温度变化，温度传感器的传感元件通常采用热敏电阻，当反应体系温度发生微小变化时其电阻值发生变化，具有测量电阻不需要接触溶液、一支电极适合各种类型的滴定、测定快速、分辨率高、操作简单、结果准确、温度传感系统维护方便等特点，缺点是不适合复杂体系测定。光谱滴定是通过分析透过溶液的可见光信号变化，分析反应进程的非破坏性测量手段，具有响应速度快、测量范围广、操作简单、结构准确的优势，缺点是只能表征呈色物质的结构变化，标识呈色化学反应。
目前，国内外滴定分析技术都是将温度滴定方法、光谱滴定方法和电化学滴定法单独形成一套仪器，无法为同一化学反应过程提供同步测定结果，也无法进行不同测定结果之间的同步数据比较，而这种基于相同测量条件的数据比较对于物质结构的表征分析十分重要。三种方法各有优缺点，将三种方法集成为统一的一种测量技术，是分析行业内的一大进步。此前，由于技术的原因，没有仪器具备同步测量温度、可见光光谱和电化学滴定数据的能力，不能满足化学分析中获得不同方法的同步测量数据的要求，只能采用单 独实验单独参数的测定，其缺陷在于：1)由于测量对象的不统一，单独实验时每次实验的基质和测量条件不尽相同，所以每次的化学反应的数据也不尽相同，进而在基于不同的实验数据进行比对分析时，获得的化学反应信息会存在误差；2)较少的样品量无法满足多次单独实验的样品需求，且多次单独实验也增加了实验步骤，延长了实验时间，影响实验进程。
因此，开发一种可以为同一化学反应过程提供多种滴定模式同步测定的光谱-电位-温度多维滴定分析仪及其使用方法成为了本领域技术人员亟需解决的问题。
发明内容
有鉴于此，本发明的目的是针对现有技术中存在的问题，提供一种可以为同一化学反应过程提供同步测定结果的光谱-电位-温度多维滴定分析仪，该光谱-电位-温度多维滴定分析仪可以满足化学分析中不同分析方法的同步测量要求，提高了不同测量方法之间的测量精度，有效减少了多次单独实验的工作量，可以实现针对同一分析对象、不同分析方法的同步测量。
为了实现上述目的，本发明采用如下技术方案：
一种光谱-电位-温度多维滴定分析仪，包括试剂控制系统、滴定测量系统和数据处理系统，所述试剂控制系统通过所述滴定测量系统与所述数据处理系统连接；
所述试剂控制系统包括试剂舱和测量舱，所述试剂舱和所述测量舱通过试剂管路连通；
所述滴定测量系统包括光谱滴定测量装置、温度滴定测量装置和电位滴定测量装置，且所述光谱滴定测量装置、温度滴定测量装置和电位滴定测量装置并联设置于所述测量舱内部；
所述数据处理系统包括测量信号转换及计算装置，所述测量信号转换及计算装置分别与所述光谱滴定测量装置、所述温度滴定测量装置、所述电位滴定测量装置通过信号连接。
值得说明的是，至少一个所述测量舱与至少一个所述试剂舱连通，示范性的，在一些情况下，一个所述测量舱与多个所述试剂舱连通；在另一些情况下，多个所述测量舱与一个所述试剂舱连通。
在滴定化学分析中，反应溶液中物质结构的变化与计量是化学分析的基础，而光谱滴定、温度滴定和电位滴定则是分别用不同物理量为化学反应及其中的物质结构变化提供结构特征信息。
考虑到化学反应中物质结构的变化常会显示为反应溶液的颜色变化，因此在光谱滴定过程中，随着滴定剂的不断加入和反应的进程，化学反应中的物质结构不断发生变化，不同的结构对可见光光谱不同波长的吸收能力存在差异，从而导致反应溶液的颜色发生相应的变化，此时，用不同参数和衍生参数对变化的条件进行标识，可以用滴定曲线标识和/或表征化学反应及其中的物质结构变化和变化过程。
而电位滴定法是依据反应溶液中不同结构的物质其电化学电位的变化表征化学反应的进行。在电位滴定过程中，随着滴定剂的不断加入，反应进程中的参与化学反应的物质结构产生变化，其结构的电极电位Es不断发生变化，当电极电位发生预定的突跃时，说明滴定到达终点，此时，用不同参数和衍生参数对变化的条件进行标识和/或表征化学反应及其中的物质结构变化和变化过程。
同时，考虑到还有部分化学反应会伴随着吸热和放热，这种温度的改变被称为焓变(ΔH)，其原理公式为：ΔH＝ΔG+TΔS，其中，ΔG是自由能变化量，T是反应体系的温度，ΔS是熵的变化量。因此，随着温度滴定反应的发生，热量被释放到环境中或从环境中吸收，溶液的温度会上升或下降，此时，以温度为测量参数可以标识和/或表征化学反应及其中的物质结构变化和变化过程。
因此，当使用光谱滴定技术、电位滴定技术和温度滴定技术三种滴定方法对相同测量环境及状态下的同一反应进程进行同步测量时，电位滴定技术和温度滴定技术作为成熟的化学分析测量技术，理论上不会降低单独仪器测量的精密度和准确度；光谱滴定技术作为发明人的新发明技术，其应用方面 正可以对前述成熟技术进行验证，并且在数据噪音、数据校正、测量曲线处理等方面得到新的应用。
值得说明的是，本发明将三种技术集合在同一仪器上，与现有的单一技术单独一种仪器相比，在结构上共用试剂系统和数据处理装置，可以明显的降低仪器成本；三种测量方法的数据进行同步比较，可以得到针对相同测定目标、且不存在相对误差的多维测量数据，通过不同测量技术数据之间的比较分析，可以为化学反应中物质结构的变化过程提供不同的角度、不同表征参数的分析结果，提高不同测量方法之间的精度和分析方法的正确度，有效减少滴定分析的工作量，有可能获得更准确的测量方法和发现新的物质物理特性和结构数据。本发明采用同一反应过程的多维同步分析技术，为分析化学提供一种新的分析技术平台。
优选的，所述试剂舱包括滴定液储存容器、试剂控制装置和第一温度控制装置，所述滴定液储存容器与所述试剂控制装置通过试剂管路连通，所述第一温度控制装置与所述滴定液储存容器连接；
所述试剂控制装置包括保护气组件、气体过滤组件和液体感应组件，且所述保护气组件为所述滴定液储存容器中的滴定试剂提供保护气环境，所述气体过滤组件用以实现空气气体的过滤，所述液体感应组件感应所述滴定液储存容器中的滴定液余量；
所述第一温度控制装置包括加热组件、降温组件和温度感应组件，且所述第一温度控制装置为所述滴定试剂提供恒温环境。
值得说明的是，所述保护气组件包括保护气管路和阀门，所述至少一个保护气管路包括至少一个保护气进口和至少一个阀门。
值得说明的是，所述气体过滤组件包括净化剂容器、空气管路、净化气管路和多个阀门，空气经所述空气管路进入所述净化剂容器，根据滴定需要，通过净化剂去除空气中的干扰物质，例如二氧化碳、氧气或水等，经过过滤的洁净气体再通过净化气管路进入滴定液储存容器；所述空气管路、净化气管路上均设置有阀门，以调控气路开闭、气流速度。
值得说明的是，所述液体感应组件包括磁性传感器和非接触传感器；所述磁性传感器设置于所述滴定液储存容器外壁，用以感应所述滴定液储存容器中的滴定液液面高度；所述非接触传感器设置于所述滴定液储存容器瓶口，用以感应所述滴定液储存容器中的溶液体积信息。
现有技术中，滴定试剂的储存温度与环境温度基本同步，对于一些不稳定的、对温度敏感的试剂，当环境温度变化时，有可能产生结晶、沉淀、产气、挥发等变化，致使试剂溶液的浓度及稳定性发生变化，影响测定结果。本发明通过试剂舱中第一温度控制装置的设置，将环境温度对储存试剂的影响降低，根据设定将储存试剂保持需要的高温或者低温进行恒温保存，还可以基于滴定测定的需要对滴定液预先进行升温或降温处理，有益于化学滴定的进行。
并且，考虑到空气中干扰未知，例如二氧化碳、氧气等容易与滴定试剂发生化学反应，进而会导致滴定试剂的性质改变，本发明通过试剂控制装置的保护气组件、气体过滤组件的设置为滴定试剂提供经过过滤的洁净气体和惰性气体的保护环境，从而避免空气中反应性气体对滴定试剂的影响。
进一步值得说明的是，所述滴定液储存容器、所述净化剂容器分别带有密封容器口，以避免滴定液、净化剂与外界发生物质交换，保证滴定液、净化剂储存环境条件的稳定性。
优选的，所述测量舱包括机械臂、滴定头、滴定控制装置、反应容器、搅拌装置、清洗装置、第二温度控制装置、气体保护装置和反馈信号装置；
所述滴定头与所述测量舱壁通过所述机械臂连接，以实现所述滴定头与所述反应容器的相对位移；
所述滴定控制装置、所述搅拌装置、所述清洗装置、所述气体保护装置分别与所述滴定头连接，并通过所述滴定头实现与所述反应容器的相对位移；
所述反馈信号装置分别与所述机械臂、所述滴定控制装置、搅拌装置、清洗装置、第二温度控制装置、气体保护装置通过信号连接，且所述第二温度控制装置用于控制滴定反应的容器温度，所述气体保护装置用于为滴定反应提供保护气环境；
所述滴定控制装置与所述试剂控制装置通过管路连通，所述反馈信号装置与所述测量信号转换及计算装置信号连接。
值得说明的是，所述反应容器侧壁上设置有溶液溢流孔，用以保证反应容器中的反应溶液不会从反应容器上沿溢出，所述反应容器的外部还设置有废液收集盘，用以收集从所述溶液溢流孔中溢出的溶液，所述废液收集盘包括废液出口，所述溢出的溶液通过所述废液出口排出测量舱。
值得说明的是，所述清洗装置包括清洗液组件和清洗气组件，所述清洗液组件通过喷淋清洗液冲洗浸入反应溶液中的搅拌装置、光信号传感器、温度信号传感器及电位信号传感器，所述清洗气组件通过洁净空气或惰性气体吹洗浸入反应溶液中的搅拌装置、光信号传感器、温度信号传感器及电位信号传感器。
值得说明的是，所述滴定控制装置包括至少一个试剂加入组件和液面距离传感器，通过所述试剂加入组件的开闭控制滴定试剂加入的速度、种类、加入时间，通过所述液面距离传感器控制所述滴定头与所述反应容器的距离。
考虑到多维滴定仪的半自动化、批量化的使用，本发明通过机械臂和滴定头的集成化设置，实现了滴定控制装置、搅拌装置、清洗装置和气体保护装置与反应容器的相对位移，从而避免了现有仪器使用时频繁的人工操作，进而提高了分析速度，减少了分析人员工作量。
为了调控滴定反应条件，本发明通过测量舱中滴定控制装置调节滴定试剂的加入速度、加入试剂种类或加入的时间点；通过搅拌装置的设置保证反应溶液体系的均匀，从而实现滴定测量的准确；并且，考虑到多维滴定仪的自动化及滴定测量的连续性，本发明通过所述清洗装置与所述反应容器、搅拌装置的管路连接，避免了连续多次测量时反应溶液的交叉污染，为连续测定创造了测量质量保证条件。
并且，考虑到在一些滴定反应测定时，反应温度、反应气氛都对滴定反应的测定具有重要影响。例如测量食品中还原糖的实验需要在沸腾状态下对样品进行滴定，此时，常温反应环境已不能满足测定条件需要；再例如在油脂的过氧化值测定中，空气中的氧气可氧化油脂，影响过氧化值的测定，此 时，惰性气氛的存在就对反应测定结果的准确性产生了重要影响。因此，本发明通过第二温度控制装置和气体保护装置的设置，保证了滴定反应环境可以根据滴定反应的不同进行调节，从而保证了多维滴定仪的广泛适用性，以及反应测定结果的准确性。
更为优选的，所述温度滴定测量装置包括温度信号传感器，所述电位滴定测量装置包括电位信号传感器，所述光谱滴定测量装置包括光信号传感器，且所述温度信号传感器、电位信号传感器、光信号传感器与所述反应容器通过信号连接；
所述温度信号传感器、电位信号传感器与所述滴定头连接，并通过所述滴定头实现与所述反应容器的相对位移；
所述光谱滴定测量装置还包括光源和光信号加载部件，所述光源、所述光信号加载部件与所述光信号传感器通过光信号顺次连接。
值得说明的时，所述光源为发射波长为380nm～780nm的不间断连续光源，通过所述光源发出的的一种、几种或全部波长的光信号通过光信号加载部件射向化学反应溶液，经化学反应溶液的吸收和/或反射后，再经光信号传感器向所述测量信号转换及计算装置提供光谱测量信息。
在多维滴定测定的过程中，所述温度信号传感器、电位信号传感器、光信号传感器可以独立的或者同步检测反应容器中的滴定反应。当对三者的测量周期进行同步设定后，每个计量点的测量数据都可以视为同一反应体系同一时刻的、不同测量模式的测量数据。此时，将同一测量模式的不同计量点的测量数据，或者同一计量点的不同测量模式的测量数据进行比较分析，可以得到基于相同测量条件的不同理化参数的物质结构表征信息，从而实现反应溶液中物质结构的变化表征与计量分析。
进一步优选的，所述光信号加载部件包括光透镜，所述光透镜设置于所述反应容器的外壁。
值得说明的是，所述光透镜可以为一个或多个，一种情况下，所述的一个光透镜在所述反应容器的一侧外壁；另一种情况下，所述的两个光透镜平行设置于所述反应容器的外壁，且所述的第一光透镜在所述反应容器的一侧 外壁，所述的第二光透镜在所述反应容器相对一侧的外壁，所述光源、第一光透镜和第二光透镜顺次在一条直线上。
更进一步优选的，所述光信号加载部件还包括反射镜，所述反射镜设置于所述反应容器的外壁或内部。
示范性地，一些应用场景中，所述反射镜位于所述反应容器的内部，光源发出的测量光线经反应容器外壁的光透镜射向反应溶液后，经反应溶液内部的反射镜反射，再通过光透镜射向所述光信号传感器，所述光源、光透镜和反射镜顺次在一条直线上；
示范性地，另一些应用场景中，所述反射镜位于所述反应容器的外壁，光源发出的测量光线经反应容器外壁的第一光透镜射向反应溶液后，经反应容器另一侧外壁的第二光透镜射向位于反应容器外壁的反射镜，反射后，再穿过反应溶液经第一光透镜射向所述光信号传感器，所述光源、第一光透镜、第二光透镜和反射镜顺次在一条直线上。
优选的，所述化学反应用光谱-电位-温度多维滴定分析仪还包括数据输出显示系统，所述数据输出显示系统与所述数据处理系统连接，以实现多维滴定参数的同步输出与显示。
本发明的另一目的在于提供所述光谱-电位-温度多维滴定分析仪的使用方法。
为了实现上述目的，本发明提供如下技术方案：
一种光谱-电位-温度多维滴定分析仪的滴定方法，包括以下步骤：
S1、仪器开机启动；
S2、设置试剂舱环境参数，利用第一温度控制装置调控试剂舱温度，并利用试剂控制装置中的气体过滤组件实现空气气体的过滤，利用试剂控制装置中的保护气组件为滴定试剂提供保护气环境；
S3、设置测量舱环境参数，利用滴定控制装置设定滴定试剂的滴定参数，利用第二温度控制装置调控测量舱温度，并利用气体保护装置为反应容器充入保护气；
S4、测定前预处理：进行仪器基准校正，并配制被滴定液于反应容器中，备用；
S5、设置测定参数：在数据处理系统中设定至少一种计量参数，选定光谱滴定模式、温度滴定模式、电位滴定模式中的一种或多种，并选择滴定模式中至少一种测量参数；
S6、待测反应的测定：将滴定液储存容器中的滴定试剂通过试剂控制装置和滴定控制装置加入反应容器，与步骤S4得到的被滴定液反应，利用光谱滴定测量装置、温度滴定测量装置、电位滴定测量装置中的一种或多种同步测量反应容器中的反应溶液，得到与步骤S5中设置的计量参数、测量参数相对应的测量数据；
S7、利用数据处理系统存储分析步骤S6中得到的测量数据，并利用数据输出显示系统同步显示测量数据；
S8、滴定完成后，反馈信号装置终止滴定控制装置、气体保护装置、搅拌装置及第二温度控制装置的工作，并开启清洗装置，以清洗浸入反应溶液中的搅拌装置及光信号传感器、温度信号传感器、电位信号传感器。
值得说明的是，步骤S3中所述的滴定试剂的滴定参数包括滴定试剂的滴定速率、滴定时间、滴定种类中的一种或多种。
值得说明的是，步骤S5中所述的计量参数包括时间t及其衍生参数、脉冲信号f及其衍生参数、反应液的pH值及其衍生参数、加入试剂体积V及其衍生参数、反应液的物质浓度C及其衍生参数、电位滴定参数Es及其衍生参数、温度滴定参数T及其衍生参数、光谱滴定参数S及其衍生参数中的一种或多种。可以理解的，计量参数是为明确测量点、构建滴定曲线而选择的测量基准，现有技术中多选择时间t或加入试剂体积V作为测量基准，但在实际滴定分析中，研究人员往往需要对同一化学反应进行化学计量学、化学热力学及反应动力学等不同表征参数的计算。因此，不同计量参数的选取对滴定分析的信息采集及测量数据处理具有十分重要的影响。因此，基于对现有滴定分析方法以及反应溶液中物质结构的变化与计量的考量，本发明对计量参数的选择作具体限定，但应理解，本领域普通技术人员在没有做出创造性 劳动前提下所获得的所有其他计量参数及其衍生参数，都属于本发明保护的范围。
并且，考虑到步骤S5中选定光谱滴定模式、温度滴定模式、电位滴定模式中的一种或多种进行多维滴定分析，本发明所述的测量参数包括电位滴定模式中电位滴定参数Es及其衍生参数、温度滴定模式中温度滴定参数T及其衍生参数、光谱滴定模式中光谱滴定参数S及其衍生参数中的一种或多种。
其中，所述衍生参数是以设定的至少一种计量参数或至少一种测量参数为自变量参数，通过本领域公知的计算方法，经过至少一次计算得到任意一种因变量参数。应当理解，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他计量参数或测量参数的衍生参数，都属于本发明保护的范围。
优选的，步骤S5中所述的光谱滴定模式的测量方式包括全透射模式、全透射-全反射模式、半透射-半反射模式或反射式模式。
值得说明的是，全透射模式属于非接触式测量方式，是光源光从装有第一光学透镜的反应容器一侧进入反应容器，光源光的部分波长光在反应溶液中被吸收，之后，加载了吸收信号的信号光从反应容器相对一侧通过第二光学透镜射出反应容器，通过光信号传感器将光谱信息导入测量信号转换及计算装置，以得到反应溶液的吸收信息；
全透射-全反射模式属于非接触式测量方式，是光源光从装有第一光学透镜的反应容器一侧进入反应容器，光源光的部分波长光在反应溶液中被吸收，加载了吸收信号的信号光从反应容器相对一侧通过第二光学透镜射出反应溶液后，被设置于反应容器外壁的反射镜将信号光反射再次进入反应溶液中，再次被吸收并加载吸收信号，然后从第一光学透镜射出反应容器，通过光信号传感器将光谱信息导入测量信号转换及计算装置，以得到反应溶液的吸收信息。所述全透射-全反射模式一次测量过程有2次加载吸收信号的过程，以实现信号强度的增加；
半透射-半反射模式属于接触式测量方式，光源光从光透镜进入反应溶液中，光源光的部分波长光在反应溶液中被吸收，加载了吸收信号后的信号光 由溶液内部的反射镜反射回光透镜，射出反应容器，通过光信号传感器将光谱信息导入测量信号转换及计算装置，以得到反应溶液的吸收信息；
反射式模式属于非接触式测量方式，光源光从光透镜进入反应溶液中，光源光的部分波长光由反应溶液表面吸收，加载了吸收信号的信号光在溶液表面被反射出反应容器，通过光信号传感器将光谱信息导入测量信号转换及计算装置，以得到反应溶液的吸收信息。
优选的，步骤S5中所述的温度滴定模式的测量方式包括浸入接触式、贴壁接触式、溶液表面照射式或容器表面照射式。
值得说明的是，所述浸入接触式是将传感器浸没在反应溶液中，反应溶液的温度变化直接传导给温度传感器；
所述贴壁接触式属于接触式测量，是将温度传感器紧贴在反应容器的外壁，反应溶液的温度变化传导给反应容器后，再经反应容器传导给温度传感器；
所述溶液表面照射式属于非接触式测量，是将反应溶液表面辐射的红外能量信号聚焦在温度传感器上并转变为相应的电信号；
所述容器表面照射式属于非接触式测量，是将反应溶液的热量变化传导至反应容器表面，反应容器表面辐射的红外能量信号聚焦在温度传感器上并转变为相应的电信号。
本发明的工作原理为：在同一测定过程中，将光谱滴定测量装置、电位滴定测量装置和温度测量装置并联，同时或者单一地进行测量参数的测量，获得相同化学反应条件下的光谱滴定参数、电位滴定参数和温度测量参数，大幅度减小甚至消除因测量条件不同而导致的不同测量模式测量参数之间的误差，减少了同一样品多次滴定的工作量，测量精度高；并利用试剂舱和测量舱的设置，统一测定环境条件，外界干扰小，提高了多维滴定的灵敏度和准确度，使测定结果更加准确可靠。
与现有技术相比，本发明的有益技术效果为：
1、将单一的滴定测量仪器改为由光谱滴定测量装置、电位滴定测量装置和温度测量装置并联设置的多维滴定仪，在不改变现有操作规程的基础上， 滴定检测过程中因测量条件不同、化学反应过程的未知性而导致的不同测量模式测量参数之间的误差可以通过统一计量点的测量参数予以实时修正，有利于减小不同滴定测量模式之间的误差，提高测量精度；
2、通过试剂舱和测量舱对滴定液储存及滴定反应环境的控制，统一了滴定环境条件，降低了外界干扰，达到改善滴定体系信噪比，提高多维滴定的检测灵敏度的目的；
3、单元功能清晰、结构简单，便于集成化、微型化，可实现滴定反应的半自动化、批量化检测；
4、可以实现同一样品的多种滴定模式的同时测定，提高分析速度，减少了分析步骤，极大的减轻了分析人员的工作量。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据提供的附图获得其他的附图。
图1为本发明提供的一种光谱-电位-温度多维滴定分析仪示意图。
图2为本发明提供的一种光谱-电位-温度多维滴定分析仪的试剂舱示意图。
图3为本发明提供的一种光谱-电位-温度多维滴定分析仪的试剂舱中试剂控制装置示意图。
图4为本发明提供的一种光谱-电位-温度多维滴定分析仪的试剂舱中试剂控制装置的保护气组件和液体感应组件示意图。
图5为本发明提供的一种光谱-电位-温度多维滴定分析仪的试剂舱中试剂控制装置的气体过滤组件示意图。
图6为本发明提供的一种光谱-电位-温度多维滴定分析仪的测量舱示意图。
图7为本发明提供的一种光谱-电位-温度多维滴定分析仪的测量舱滴定头示意图。
图8为本发明提供的一种光谱-电位-温度多维滴定分析仪的光谱滴定模式的4种测量方式的光路示意图。
图9为本发明实验例1提供的多维滴定曲线。
图10为本发明实验例2提供的电位(A)、光谱(B)、温度(C)滴定曲线。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
为更好地理解本发明，下面通过以下实施例对本发明作进一步具体的阐述，但不可理解为对本发明的限定，对于本领域的技术人员根据上述发明内容所作的一些非本质的改进与调整，也视为落在本发明的保护范围内。
实施例1
结合参考图1～8，一种多维滴定仪，包括试剂控制系统、滴定测量系统和数据处理系统，所述试剂控制系统通过所述滴定测量系统与所述数据处理系统连接。
参照图1，所述试剂控制系统包括试剂舱1和测量舱2，试剂舱1和测量舱2通过管路8连通。
参照图2，试剂舱1包括滴定液储存容器101、试剂控制装置102和第一温度控制装置103，滴定液储存容器101与试剂控制装置102通过试剂管路连通，第一温度控制装置103与滴定液储存容器101连接；
参照图3，试剂控制装置102包括保护气组件1021、气体过滤组件1022和液体感应组件1023，且保护气组件1021为滴定液储存容器101中的滴定试 剂提供保护气环境，气体过滤组件1022用以实现空气气体的过滤，液体感应组件1023感应滴定液储存容器101中的滴定液余量；
参照图4，保护气组件1021包括保护气管路10211和阀门10212，至少一个保护气管路10211包括至少一个保护气进口10213和至少一个阀门10212。
参照图5，气体过滤组件1022包括净化剂容器10221、空气管路10222、净化气管路10223和多个阀门10224，空气经空气管路10222进入净化剂容器10221，根据滴定需要，通过净化剂去除空气中的二氧化碳、氧气或水，经过过滤的洁净气体再通过净化气管路10223进入滴定液储存容器101；空气管路10222、净化气管路10223上均设置有阀门10224，以调控气路开闭、气流速度；
参照图4，液体感应组件1023包括磁性传感器10231和非接触传感器10232，磁性传感器10231设置于滴定液储存容器101外壁，用以感应滴定液储存容器101中的滴定液液面高度；非接触传感器10232设置于滴定液储存容器101的瓶口，用以感应滴定液储存容器101中的气压；
第一温度控制装置103包括加热组件、降温组件和温度感应组件，且第一温度控制装置103为所述滴定试剂提供恒温环境。
参照图6，测量舱2包括机械臂201、滴定头202、滴定控制装置203、反应容器204、搅拌装置205、清洗装置206、第二温度控制装置207、气体保护装置208和反馈信号装置209；
滴定头202与测量舱壁通过机械臂201连接，滴定控制装置203、搅拌装置205、清洗装置206、气体保护装置208分别与滴定头202连接，反馈信号装置209分别与机械臂201、滴定控制装置203、搅拌装置205、清洗装置206、第二温度控制装置207、气体保护装置208通过信号连接；
并且，滴定控制装置203与试剂控制装置102通过管路8连通；
反应容器204的侧壁上还设置有溶液溢流孔2041，用以保证反应容器204中的反应溶液不会溢出，反应容器204的外部还设置有废液收集盘2042，用 以收集从溶液溢流孔2041中溢出的溶液，废液收集盘2042包括废液出口2043，所述溢出的溶液通过废液出口2043排出测量舱2；
参照图7，清洗装置206包括清洗液组件2061和清洗气组件2062，清洗液组件2061通过喷淋清洗液冲洗浸入反应溶液中的搅拌装置205、光信号传感器504、温度信号传感器6及电位信号传感器7，清洗气组件2062通过洁净空气或惰性气体吹洗浸入反应溶液中的搅拌装置205、光信号传感器504、温度信号传感器6及电位信号传感器7；
滴定控制装置203包括至少一个试剂加入组件2031和液面距离传感器2032，通过试剂加入组件2031的开闭可以控制滴定试剂加入的速度、种类及加入时间，通过液面距离传感器2032可以控制滴定头202与反应容器204的距离。
所述滴定测量系统包括光谱滴定测量装置5、温度滴定测量装置和电位滴定测量装置，且光谱滴定测量装置5、所述温度滴定测量装置和所述电位滴定测量装置并联设置于所述测量舱2内部；光谱滴定测量装置5包括光信号传感器504，所述温度滴定测量装置包括温度信号传感器6，所述电位滴定测量装置包括电位信号传感器7，且所述温度信号传感器6、电位信号传感器7、光信号传感器504与反应容器204通过信号连接。
参照图8，所述光谱滴定测量装置5还包括光源501和光信号加载部件，所述光源501、所述光信号加载部件与光信号传感器504通过光信号顺次连接；
所述光信号加载部件包括第一光透镜502，第一光透镜502设置于反应容器204的外壁；所述光信号加载部件还包括第二光透镜503，第二光透镜503设置于反应容器204的外壁；
所述光信号加载部件还包括反射镜505，反射镜505设置于反应容器204的外壁或内部。
参照图1，所述数据处理系统包括测量信号转换及计算装置3，测量信号转换及计算装置3分别与光谱滴定测量装置5、温度滴定测量装置6、电位滴定测量装置7通过信号连接。
所述化学反应用光谱-电位-温度多维滴定分析仪还包括数据输出显示系统4，数据输出显示系统4与所述数据处理系统连接，以实现多维滴定参数的同步输出与显示。
工作时，开启仪器，确定滴定液储存容器101和净化剂容器10221中的试剂余量，调控阀门10212或阀门10224的开闭以调整气路及气流速度，并使空气进入气体过滤组件1022以去除空气中的二氧化碳、氧气或水，或引入惰性气体为滴定试剂提供保护气环境。同时，开启第一温度控制装置103恒温储存滴定试剂。
滴定准备时，将被滴定液加至反应容器204中，调整机械臂201以使滴定头202与反应容器204达到适宜的相对位置。开启第二温度控制装置207、气体保护装置208，调控测量舱2的环境参数，并通过试剂加入组件2031控制滴定试剂加入的速度、种类及加入时间。
滴定开始时，将滴定头202下移至反应容器204的瓶口处，闭合，滴定试剂通过管路8从滴定液储存容器101经试剂加入组件2031滴加至反应容器204中，开启搅拌装置205，利用光信号传感器504、温度信号传感器6、电位信号传感器7中的一种或多种进行测定。
在进行光谱滴定测量时，光谱滴定测量装置5测定反应容器204中的滴定反应，其中，全透射模式(如图8A所示)是光信号从光源501发出，经第一光学透镜502进入反应容器204，光信号的部分波长光在反应溶液中被吸收后，加载了吸收信号的光信号经由第二光学透镜503射出，通过光信号传感器504将光谱信息导入测量信号转换及计算装置3，以得到滴定反应的光谱测量信息；
反射模式(如图8B所示)是光信号从光源501发出直接进入反应容器204，光信号的部分波长光由反应溶液表面吸收，加载了吸收信号的光信号由溶液表面反射，通过光信号传感器504将光谱信息导入测量信号转换及计算装置3，以得到滴定反应的光谱测量信息；
半透射-半反射模式(如图8C所示)是光信号从光源501发出，经第一光学透镜502进入反应容器204，光信号的部分波长光在反应溶液中被吸收后， 加载了吸收信号的光信号由溶液内部的反射镜505发射，再经第一光学透镜502射出反应容器204，通过光信号传感器504将光谱信息导入测量信号转换及计算装置3，以得到滴定反应的光谱测量信息；
全透射-全反射模式(如图8D所示)是光信号从光源501发出，经第一光学透镜502进入反应容器204，光信号的部分波长光在反应溶液中被吸收后，加载了吸收信号的光信号经由第二光学透镜503射出，并被反射镜505反射再次进入反应溶液中，再次被吸收并加载吸收信号后，再从第一光学透镜502射出反应容器204，通过光信号传感器504将光谱信息导入测量信号转换及计算装置3，以得到滴定反应的光谱测量信息。
滴定完成后，测量信号转换及计算装置3向反馈信号装置209发出信号，搅拌装置205、第二温度控制装置207、气体保护装置208、试剂加入组件2031停止工作，机械臂201带动滴定头202移动，在液面距离传感器2032的信号反馈下，远离反应容器204，清洗装置206开始清洗浸入反应溶液中的搅拌装置205、光信号传感器504、温度信号传感器6及电位信号传感器7等，并通过溶液溢流孔2041将反应容器204中的反应溶液经废液收集盘2042的废液出口2043排出测量舱2，以待下一次滴定反应进行。
实施例2
一种光谱-电位-温度多维滴定分析仪的滴定方法，步骤包括：
S1、开启仪器；
S2、设置试剂舱环境参数，通过第一温度控制装置106控制试剂舱1温度、利用试剂控制装置为滴定试剂提供保护气环境，其中，保护气经气体过滤组件102过滤杂质后通过保护气组件103进入滴定液储存容器101中；
S3、设置测量舱2环境参数，利用滴定控制装置201设定滴定试剂的滴定参数，利用第二温度控制装置205调控测量舱2温度，并利用气体保护装置202为反应容器204充入保护气；
S4、测定前预处理：利用空白标准样品进行仪器基准校正，待校正完成后，配制被滴定液于反应容器204中，备用；
S5、设置测定参数：在数据处理系统中设定时间t为计量参数，选定光谱滴定模式中的全透射模式，并选择CIE 1976 L *a *b *色度学参数L *值为测量参数；
S6、待测反应的测定：将滴定液储存容器101中的滴定试剂通过试剂控制装置和滴定控制装置201加入反应容器204，与步骤S4得到的被滴定液反应，利用光谱滴定测量装置5测量反应容器204中的反应溶液的光谱信号，得到与步骤S5中设置的时间t、测量参数L *值相对应的测量数据；
S7、利用数据处理系统存储分析步骤S6中得到的测量数据，并利用数据输出显示系统4同步显示测量数据；
S8、滴定完成后，反馈信号装置206终止滴定控制装置201、气体保护装置202、搅拌装置203及第二温度控制装置205的工作，并开启清洗装置，以清洗反应容器204和搅拌装置203。
实施例3
一种光谱-电位-温度多维滴定分析仪的滴定方法，步骤如实施例2所述，不同之处在于：
S5、设置测定参数：在数据处理系统中设定脉冲信号f为计量参数，选定光谱滴定模式中的半透射-半反射模式，并选择CIE 1976 L *a *b *色度学参数a *值为测量参数，同时，选定温度滴定模式中的溶液表面照射式测定方法，并选择温度滴定参数T的衍生参数T 2为测量参数。
相应的，其余步骤与实施例2相同。
实施例4
一种光谱-电位-温度多维滴定分析仪的滴定方法，步骤如实施例2所述，不同之处在于：
S5、设置测定参数：在数据处理系统中设定加入滴定液体积V和反应溶液的物质浓度C为计量参数，选定光谱滴定模式中的反射式模式，并选择CIE 1976 L *a *b *色度学参数ΔE值为测量参数，选定温度滴定模式中的贴壁接触式测定方法，并选择温度滴定参数T的衍生参数T为测量参数，同时，选定电位滴定模式并选择电位滴定参数Es的衍生参数Es/T为测量参数。
相应的，其余步骤与实施例2相同。
为了进一步验证本发明的优异效果，发明人还进行了如下实验：
实验例1
称取110g氢氧化钠，溶于100mL无二氧化碳的水中，摇匀，注入聚乙烯容器中，密闭放置至溶液清亮，该溶液用于配置氢氧化钠溶液的储备溶液；用塑料管量取储备溶液的上层清液5.4mL，用无二氧化碳的水稀释至1000mL，摇匀，该溶液为未知浓度c的氢氧化钠标准溶液溶液。将该溶液置于实施例1光谱-电位-温度多维滴定分析仪的滴定液储存容器101中，加入保护气，开启第一温度控制装置103并读取温度参数；
将工作基准试剂邻苯二甲酸氢钾(摩尔质量为克每摩尔(g/mol)[M(KHC 8H 4O 4)＝204.22])于105℃～110℃电烘箱中，干燥至恒重，在精度大于0.1mg的天平上称取(m)邻苯二甲酸氢钾0.7526g，用80mL无二氧化碳的水溶解成邻苯二甲酸氢钾溶液。将该溶液转移至反应容器204中，该溶液为待测样品溶液。
称取1g酚酞指示剂，用乙醇(95％)溶解、稀释、定容至100mL。
关闭第二温度控制装置207，启动气体保护装置208，以水充满反应容器204为测量用空白样品；清洗滴定浸入液面的部件，备用。
设置通用参数：设置测量周期为0.2s，最小加入试剂体积10μL，最大滴加体积100μL，搅拌速度200转/秒。
设置测定参数：启动钨灯光源并稳定至光通量稳定，选择全透射式测量模式，光谱范围380nm～780nm，间隔5nm，积分时间≤2，狭缝宽度≤5.0，以水调整装置的空白值，测量数据采集光谱透射比；选择酸碱滴定模式，pH电极，测量数据采集电位滴定参数Es；选择接触侵入式模式，温度电极，测量数据采集温度滴定参数T。
在与待测样品溶液等量的水中加入2滴酚酞指示剂，以该溶液为样品空白进滴定，用未知浓度的氢氧化钠标准溶液对其进行滴定，达到滴定终点消耗的未知浓度的氢氧化钠标准溶液为空白试验体积数V 白；
将待测样品溶液中加入2滴酚酞指示剂，得到被滴定液，用未知浓度的氢氧化钠标准溶液对其进行滴定，达到滴定终点消耗的未知浓度c的氢氧化钠标准溶液为待测样品试验体积数V。
测量时的试剂温度为25℃，实验空白消耗的V 白试剂体积数为0.05ml，滴定数据如表1所示。
表1
Figure PCTCN2019097096-appb-000001
Figure PCTCN2019097096-appb-000002
以滴定体积为横坐标，测量参数为纵坐标绘制的滴定曲线如图9所示，到达滴定终点时，电位滴定终点峰值对应的未知浓度的氢氧化钠标准溶液体 积数为32.85ml，光谱滴定终点峰值对应的未知浓度的氢氧化钠标准溶液体积数为32.80ml，温度终点终点峰值对应的未知浓度的氢氧化钠标准溶液体积数为32.90ml。将实验空白消耗的V 白、滴定消耗的体积数换算为温度为20℃的标准体积后，按照下列公式分别计算电位滴定方法、光谱滴定方法、温度终点方法的氢氧化钠标准溶液浓度，
Figure PCTCN2019097096-appb-000003
通过计算可知，电位滴定方法测量的未知浓度c的氢氧化钠标准溶液为cEs＝0.1125mol/L；光谱滴定方法测量的未知浓度c的氢氧化钠标准溶液为cs＝0.1127mol/L；温度终点方法测量的未知浓度c的氢氧化钠标准溶液为cT＝0.1123mol/L；一种光谱-电位-温度多维滴定分析仪的滴定的标准偏差(S)为0.0002，相对标准偏差(RSD％)为0.18％。
实验例2
称取110g氢氧化钠，溶于100mL无二氧化碳的水中，摇匀，注入聚乙烯容器中，密闭放置至溶液清亮，该溶液用于配置氢氧化钠溶液的储备溶液；用塑料管量取储备溶液的上层清液5.4mL，用无二氧化碳的水稀释至1000mL，摇匀，该溶液为未知浓度的氢氧化钠标准溶液溶液。
将工作基准试剂邻苯二甲酸氢钾于105℃～110℃电烘箱中，干燥至恒重，在精度大于0.1mg的天平上称取邻苯二甲酸氢钾0.7555g、0.7587g、0.7516g用于电位滴定、光谱滴定和温度滴定，分别用80mL无二氧化碳的水溶解成邻苯二甲酸氢钾溶液。
称取1g酚酞指示剂，用乙醇(95％)溶解、稀释、定容至100mL。
分别使用市售电位滴定仪、温度滴定仪，及专利公开号为CN 106645134 A的化学分析用颜色测定仪进行滴定测定。滴定参数设置于实验例1相同。
在与待测样品溶液等量的水中加入2滴酚酞指示剂，以该溶液为样品空白进滴定，用未知浓度的氢氧化钠标准溶液对其进行滴定，达到滴定终点消耗的未知浓度的氢氧化钠标准溶液为空白试验体积数V 白；
将待测样品溶液中加入2滴酚酞指示剂，得到被滴定液，用未知浓度的氢氧化钠标准溶液对其进行滴定，达到滴定终点消耗的未知浓度的氢氧化钠标准溶液为待测样品试验体积数V。
测量时的试剂温度为25℃，实验空白消耗的V 白试剂体积数为0.05ml，滴定数据如表2所示。
表2
滴定体积(ml) 电位滴定Es 光谱滴定S 温度滴定T
30.00 265 365546 2
30.05 624 35622 1
30.10 0 22651 1
30.15 2 324868 1375
30.20 0 20839 5499
30.25 0 41447 1784
30.30 852 7458 170
30.35 2621 91 17
30.40 2383 2543 29
30.45 1250 1187 2
30.50 2160 161077 29
30.55 2621 30502 629
30.60 852 3880 21214
30.65 138 125191 986
30.70 328 15142 1793
30.75 220 637 977
30.80 106 32947 660
30.85 393 104723 162
30.90 640 38483 2485
30.95 393 18554 10004
31.00 467 94295 14591
31.05 393 136577 151651
31.10 467 6609 24904
31.15 467 9110 6425
31.20 549 19382 109758
31.25 393 352 41269
31.30 270 142 6671
31.35 640 394 16875
31.40 640 184 13805
31.45 973 29 145963
31.50 640 471 40556
31.55 640 24 11689
31.60 973 101476 101
31.65 973 5557 47
31.70 973 4807 40
31.75 1406 27257 318
31.80 1250 509 323
31.85 1575 8610 24
31.90 1575 2633 125
31.95 2160 3 192
32.00 2621 90539 162
32.05 2875 46224 111
32.10 4746 11663 40
32.15 6361 35475 40
32.20 5514 9051 39172
32.25 10612 2269 2010
32.30 15609 251811 87487
32.35 24061 200937 175648
32.40 40960 12683 69284
32.45 62295 5673 25781
32.50 87418 4001 174910
32.55 121670 19261 608207
32.60 68590 3585 27589
32.65 13310 110733 364859
32.70 3430 482832 106
32.75 26281 1763378 3312994
32.80 95281 35 1643545
32.85 14049 10688 1488596
32.90 155165 15752 1237759
32.95 2314755 4 9
33.00 2160 19854 16638
33.05 5927 78 69121
33.10 124872 3606 108483
33.15 346460 735599 62501
33.20 3144 123054 61661
33.25 238879 165656 52616
以滴定体积为横坐标，测量参数为纵坐标绘制的滴定曲线如图10所示，其中，A为电位滴定曲线，B为光谱滴定曲线，C为温度滴定曲线，可以看到，到达滴定终点时，电位滴定终点峰值对应的未知浓度的氢氧化钠标准溶液体积数为32.95ml，光谱滴定终点峰值对应的未知浓度的氢氧化钠标准溶液体积数为32.75ml，温度终点终点峰值对应的未知浓度的氢氧化钠标准溶液体积数 为32.75ml。将实验空白消耗的V 白、滴定消耗的体积数换算为温度为20℃的标准体积后，按照下列公式分别计算电位滴定方法、光谱滴定方法、温度终点方法的氢氧化钠标准溶液浓度，
Figure PCTCN2019097096-appb-000004
通过计算可知，电位滴定方法测量的未知浓度c的氢氧化钠标准溶液为c Es＝0.1126mol/L；光谱滴定方法测量的未知浓度c的氢氧化钠标准溶液为c s＝0.1137mol/L；温度终点方法测量的未知浓度c的氢氧化钠标准溶液为c T＝0.1127mol/L；对于相同未知浓度的氢氧化钠标准溶液三种滴定方法的标准偏差(S)为0.0006、相对标准偏差(RSD％)为0.54％。
由实验例1、2的数据可知，本发明将单一的滴定测量仪器改为由光谱滴定测量装置、电位滴定测量装置和温度测量装置并联设置的多维滴定仪，在不改变现有操作规程的基础上，滴定检测过程中因测量条件不同、化学反应过程的未知性而导致的不同测量模式测量参数之间的误差可以通过统一计量点的测量参数予以实时修正，将三种滴定方法见的标准偏差(S)由0.0006降为0.0002，相对标准偏差(RSD％)由0.54％降至0.18％，具有显著的统计学差异，有利于减小不同滴定测量模式之间的误差，提高测量精度。并且，本发明可以实现同一样品的多种滴定模式的同时测定，提高分析速度，减少了分析步骤，极大的减轻了分析人员的工作量。
对所公开的实施例的上述说明，使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下，在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。

Claims (10)

  1. 一种光谱-电位-温度多维滴定分析仪，包括试剂控制系统、滴定测量系统和数据处理系统，所述试剂控制系统通过所述滴定测量系统与所述数据处理系统连接，其特征在于：
    所述试剂控制系统包括试剂舱和测量舱，所述试剂舱和所述测量舱通过试剂管路连通；
    所述滴定测量系统包括光谱滴定测量装置、温度滴定测量装置和电位滴定测量装置，且所述光谱滴定测量装置、温度滴定测量装置和电位滴定测量装置并联设置于所述测量舱内部；
    所述数据处理系统包括测量信号转换及计算装置，所述测量信号转换及计算装置分别与所述光谱滴定测量装置、所述温度滴定测量装置、所述电位滴定测量装置通过信号连接。
  2. 根据权利要求1所述的一种光谱-电位-温度多维滴定分析仪，其特征在于，所述试剂舱包括滴定液储存容器、试剂控制装置和第一温度控制装置，所述滴定液储存容器与所述试剂控制装置通过试剂管路连通，所述第一温度控制装置分别与所述滴定液储存容器、所述试剂控制装置连接；
    所述试剂控制装置包括保护气组件、气体过滤组件和液体感应组件，且所述保护气组件为所述滴定液储存容器中的滴定试剂提供保护气环境，所述气体过滤组件用以实现空气气体的过滤，所述液体感应组件感应所述滴定液储存容器中的滴定液余量；
    所述第一温度控制装置包括加热组件、降温组件和温度感应组件，且所述第一温度控制装置为所述滴定试剂提供恒温环境。
  3. 根据权利要求2所述的一种光谱-电位-温度多维滴定分析仪，其特征在于，所述测量舱包括机械臂、滴定头、滴定控制装置、反应容器、搅拌装置、清洗装置、第二温度控制装置、气体保护装置和反馈信号装置；
    所述滴定头与所述测量舱壁通过所述机械臂连接，以实现所述滴定头与所述反应容器的相对位移；
    所述滴定控制装置、所述搅拌装置、所述清洗装置、所述气体保护装置分别与所述滴定头连接，并通过所述滴定头实现与所述反应容器的相对位移；
    所述反馈信号装置分别与所述机械臂、所述滴定控制装置、搅拌装置、清洗装置、第二温度控制装置、气体保护装置通过信号连接，且所述第二温度控制装置用于控制滴定反应的容器温度，所述气体保护装置用于为滴定反应提供保护气环境；
    所述滴定控制装置与所述试剂控制装置通过管路连通，所述反馈信号装置与所述测量信号转换及计算装置信号连接。
  4. 根据权利要求3所述的一种光谱-电位-温度多维滴定分析仪，其特征在于，所述温度滴定测量装置包括温度信号传感器，所述电位滴定测量装置包括电位信号传感器，所述光谱滴定测量装置包括光信号传感器，且所述温度信号传感器、电位信号传感器、光信号传感器与所述反应容器通过信号连接；
    所述温度信号传感器、电位信号传感器与所述滴定头连接，并通过所述滴定头实现与所述反应容器的相对位移；
    所述光谱滴定测量装置还包括光源和光信号加载部件，所述光源、所述光信号加载部件与所述光信号传感器通过光信号顺次连接。
  5. 根据权利要求4所述的一种光谱-电位-温度多维滴定分析仪，其特征在于，所述光信号加载部件包括光透镜，所述光透镜设置于所述反应容器的外壁。
  6. 根据权利要求5所述的一种光谱-电位-温度多维滴定分析仪，其特征在于，所述光信号加载部件还包括反射镜，所述反射镜设置于所述反应容器的外壁或内部。
  7. 根据权利要求1所述的一种光谱-电位-温度多维滴定分析仪，其特征在于，所述化学反应用光谱-电位-温度多维滴定分析仪还包括数据输出显示系统，所述数据输出显示系统与所述数据处理系统连接，以实现多维滴定参数的同步输出与显示。
  8. 如权利要求1～7任一所述的光谱-电位-温度多维滴定分析仪的使用方法，其特征在于，包括以下步骤：
    S1、仪器开机启动；
    S2、设置试剂舱环境参数，利用第一温度控制装置调控试剂舱温度，并利用试剂控制装置中的气体过滤组件实现空气气体的过滤，利用试剂控制装置中的保护气组件为滴定试剂提供保护气环境；
    S3、设置测量舱环境参数，利用滴定控制装置设定滴定试剂的滴定参数，利用第二温度控制装置调控测量舱温度，并利用气体保护装置为反应容器充入保护气；
    S4、测定前预处理：进行仪器基准校正，并配制被滴定液于反应容器中，备用；
    S5、设置测定参数：在数据处理系统中设定至少一种计量参数，选定光谱滴定模式、温度滴定模式、电位滴定模式中的一种或多种，并选择滴定模式中至少一种测量参数；
    S6、待测反应的测定：将滴定液储存容器中的滴定试剂通过试剂控制装置和滴定控制装置加入反应容器，与步骤S4得到的被滴定液反应，利用光谱滴定测量装置、温度滴定测量装置、电位滴定测量装置中的一种或多种同步测量反应容器中的反应溶液，得到与步骤S5中设置的计量参数、测量参数相对应的测量数据；
    S7、利用数据处理系统存储分析步骤S6中得到的测量数据，并利用数据输出显示系统同步显示测量数据；
    S8、滴定完成后，反馈信号装置终止滴定控制装置、气体保护装置、搅拌装置及第二温度控制装置的工作，并开启清洗装置，以清洗浸入反应溶液中的搅拌装置及光信号传感器、温度信号传感器、电位信号传感器。
  9. 根据权利要求8所述的光谱-电位-温度多维滴定分析仪的使用方法，其特征在于，步骤S5中所述的光谱滴定模式的测量方式包括全透射模式、全透射-全反射模式、半透射-半反射模式或反射式模式。
  10. 根据权利要求8所述的光谱-电位-温度多维滴定分析仪的使用方法，其特征在于，步骤S5中所述的温度滴定模式的测量方式包括浸入接触式、贴壁接触式、溶液表面照射式或容器表面照射式。
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