CN105738438A - Instrument and method for fast detecting bicarbonate radical and carbonate radical in water through double-electrode method - Google Patents
Instrument and method for fast detecting bicarbonate radical and carbonate radical in water through double-electrode method Download PDFInfo
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
The invention relates to an instrument and method for fast detecting a bicarbonate radical and a carbonate radical in water through a double-electrode method. The instrument is used for fast detecting the bicarbonate radical and the carbonate radical in underground water, surface water and seawater and comprises a microprocessor with a built-in intelligent temperature compensation and quantitative calculation software algorithm, a pH electrode, a carbon dioxide electrode, a signal conditioning unit, a temperature collecting unit, a human-computer interaction unit and a load power source management unit, wherein the load power source management unit is responsible for converting battery voltage into load circuit work voltage, the pH electrode and the carbon dioxide electrode are connected with input of the signal conditioning unit, output of the signal conditioning unit is connected with collection pins of the microprocessor, the temperature collecting unit is connected with collection pins of the microprocessor, and the human-computer interaction unit is connected with an I/O interface of the microprocessor and controls unit parameter setting and result displaying of the microprocessor to be completed. Low-power operation is achieved, power source support is not needed, and the problem that the bicarbonate radical and the carbonate radical in the water cannot be fast detected on a field site is solved.
Description
Technical field
The invention belongs to automatic test field, particularly relate to a kind of instrument and method that detected solution bicarbonate radical and carbonate are realized field quick detection.
Background technology
Bicarbonate radical and carbanion are the important parameters of survey for the purpose of locating hydrogeological resources and environmental monitoring, have important effect for analyzing formation water evolution Feature.Bicarbonate radical and carbanion are important instruction parameter in global carbon field simultaneously, it is possible to identify carbon dioxide migration feature in formation water and surface water and rule, identify escape and the situation of leakage of carbon dioxide.
At present, the measurement of bicarbonate radical and carbanion relies primarily on laboratory and completes, it is impossible to realize quick detection on-the-spot in the wild.There is the risk of secondary pollution in detected water sample acquisition process, largely weaken the verity of information measured, simultaneously from being sampled to the measuring it is generally required to longer time of laboratory, bicarbonate radical and carbanion content change, and measurement result can not represent the actual value of water sample.Current be badly in need of a kind of can bicarbonate radical and carbanion rapid detection apparatus and method in the on-the-spot water realizing quickly detection in the wild.
Summary of the invention
The main purpose of the present invention is to provide a kind of bipolar electrode method and realizes bicarbonate radical and carbonate rapid detection apparatus in water, it adopts the mode of bipolar electrode, application pH electrode and carbon dioxide electrode, microprocessor unit, load power source administrative unit, signal condition unit and the quantitative Analysis algorithm with temperature intelligent compensation, it is achieved that in subsoil water, surface water and sea water, the field condition of bicarbonate radical and carbanion quickly detects.
For achieving the above object, the present invention takes following design:
One microprocessor unit, its built-in A/D converter, and also it is built-in with the quantitative Analysis of intelligent temperature compensation and the software algorithm program of bicarbonate radical and carbanion quantitative Analysis；
One pH electrode unit, containing the pH electrode of built-in reference electrode, the electric potential signal that the output of this pH electrode is linear with the logarithm of detected solution hydrogen ion activity；
Carbon dioxide electrode unit, containing the carbon dioxide electrode of built-in reference electrode and filling liquid, the electric potential signal that the output of this electrode is linear with the logarithm of detected solution free carbon dioxide concentration；
One signal condition unit, for the scope by built-in for the output signal condition of pH electrode or carbon dioxide electrode to microprocessor unit A/D converter license；This signal condition unit is two-way, respectively for pH electrode unit and carbon dioxide unit；
One temperature collecting cell, it is made up of thermistor (temperature) sensor, constant-current source circuit and low-pass filter circuit；Described thermistor (temperature) sensor output signal after constant-current source circuit drives is connected with low-pass filter circuit；
One man-machine interaction unit, including keyboard and LCD MODULE；Described keyboard is connected with microprocessor unit I/O, is controlled for this bipolar electrode method is realized bicarbonate radical and carbonate rapid detection apparatus in water and arranges；Described LCD MODULE is connected with described microprocessor unit I/O, for display reminding information and testing result；
One load power source administrative unit, can convert battery voltage to the low pressure difference linear voltage regulator (LDO) for circuit voltage volume and No. three load switches including a battery, a road；Wherein, described low pressure difference linear voltage regulator (LDO) is powered to described microprocessor unit, and described No. three load switches control to cut out or open to think that described signal condition unit, temperature collecting cell and man-machine interaction unit provide running voltage by microprocessor unit I/O mouth；
The signal output part of described signal condition unit connects the signals collecting input of microprocessor unit；Outfan in described temperature collecting cell is connected with the signals collecting input of microprocessor unit.
Described bipolar electrode method realizes in water in bicarbonate radical and carbonate rapid detection apparatus, and described signal condition unit respectively route impedance matching circuit, low-pass filter circuit and voltage lifting circuit composition；Described pH electrode unit is connected with the impedance matching circuit input on a corresponding road respectively with carbon dioxide electrode unit outfan, after the low-pass filtered device of output signal of described impedance matching circuit, the conditioning of described voltage lifting circuit is forward voltage signal.
Described bipolar electrode method realizes in water in bicarbonate radical and carbonate rapid detection apparatus, adopts high impedance, low drifting meter specially amplifier INA121 in each impedance matching circuit of described signal condition unit.
Described bipolar electrode method realizes in water in bicarbonate radical and carbonate rapid detection apparatus, in the software algorithm program of the quantitative Analysis that intelligent temperature built-in in described microprocessor unit compensates, the temperature-compensating formula of the pH value electrode slope of this software algorithm institute foundation is:
SPph=0.1984 × TEMP+54.198 (1)
SP in formulaphFor pH electrode slope, detected solution temperature value (DEG C) instantly when TEMP is test；
The temperature compensation algorithm of the carbon dioxide electrode slope of this software algorithm institute foundation is " 1.97mV/10 DEG C；
In-situ measurement information from pH electrode and carbon dioxide electrode sends microprocessor unit to after the conditioning output of signal condition unit, and the two-way electrode data collected directly is carried out the process of temperature-compensating by this microprocessor unit；
In the software algorithm program of bicarbonate radical built-in in described microprocessor unit and carbanion quantitative Analysis, it then follows ionic dissociation equilibrium equation, computing formula is:
Wherein, K1For primary dissociation equilibrium constant, K1=10-6.352；K2For second dissociation equilibrium constant, K2=10-10.329；The concentration C of free carbon dioxideTWith detected solution hydrogen ion concentration H+By the on-the-spot test of instrument scene directly calculating conversion acquisition.
Described bipolar electrode method realizes in water in bicarbonate radical and carbonate rapid detection apparatus, and described pH electrode and carbon dioxide electrode all include reference electrode, and reference electrode is silver-silver chloride electrode.
Described bipolar electrode method realizes in water, in bicarbonate radical and carbonate rapid detection apparatus, being filled with 0.005M sodium bicarbonate filling liquid in described carbon dioxide electrode；Being equipped with the program to carbon dioxide electrode correction inside detecting instrument, the carbon dioxide electrode after this correction to program can directly record the free carbon dioxide concentration of detected solution.
Described bipolar electrode method realizes in water in bicarbonate radical and carbonate rapid detection apparatus, described microprocessor adopts MSP430 processor, and it carries 12 bit A/D converters for changing the signal of the output signal of the pH electrode after signal condition cell processing, carbon dioxide electrode output signal and temperature collecting cell output.
It is a further object of the present invention to provide a kind of bipolar electrode method and realize bicarbonate radical and carbonate method for quick in water, it quickly detects the bicarbonate radical in field condition detected solution and carbon acid ion concentration by above-mentioned detecting instrument.
For achieving the above object, the present invention takes following design:
A kind of bipolar electrode method realizes bicarbonate radical and carbonate method for quick in water, has above-mentioned bipolar electrode method and realizes bicarbonate radical and carbonate rapid detection apparatus in water；It includes following method step:
1) field investigation and sampling, starts detecting instrument, pH electrode is corrected, and is placed in detected solution by the pH electrode after correction, records the pH value of now detected solution, corresponding acquisition one path electrode data----detected solution hydrogen ion concentration H+；
2) with ion regulating agent, the pH value of detected solution is adjusted to 4～5, adjusted rear detected solution；
3) in carbon dioxide electrode, the filling liquid for buffer solution ionic strength is added, and carbon dioxide electrode is corrected, carbon dioxide electrode after correction is placed after adjustment in detected solution, records after this adjustment the concentration C of free carbon dioxide in detected solutionT；
4) the two-way electrode data H that will obtain+And CTBring ionic dissociation equilibrium equation into:
In formula: K1For primary dissociation equilibrium constant, K1=10-6.352；K2For second dissociation equilibrium constant, K2=10-10.329；
Calculate respectively and obtain bicarbonate ion concentration HCO3 -With carbon acid ion concentration CO3 2-；
5) calculated for step 4 testing result is exported, storage, printing or display.
Described bipolar electrode method realizes in water in bicarbonate radical and carbonate method for quick, and in described step 2, described ion regulating agent adopts 1M citrate buffer solution.
Described bipolar electrode method realizes in water in bicarbonate radical and carbonate method for quick, and the method in described step 3, carbon dioxide electrode being corrected is: adopt 10-2mol·L-1、10-3mol·L-1With 10-4mol·L-1Carbon dioxide standard solution carbon dioxide electrode is carried out bikini correction, before correction, carbon dioxide electrode is put in deionized water and rinses, until current potential is stable at-80mV ± 5mV；Timing, is sequentially inserted into this carbon dioxide electrode by carbon dioxide concentration of standard solution order from low to high, measures the potential value in each standard solution respectively, needs to use deionized water cleaning electrode after often having surveyed a kind of standard solution；After obtaining the magnitude of voltage of standard solution, instrument internal program utilizing method of least square automatically the logarithm of mark liquid value and the magnitude of voltage of correspondence thereof to be fitted to relation mathematic model, carbon dioxide electrode correction is complete.
A kind of bipolar electrode method of the present invention realizes bicarbonate radical and carbonate rapid detection apparatus in water and is mainly used in subsoil water, surface water and sea water bicarbonate radical and the quick detection of carbanion, it is managed by load power source, realizing super low-power consumption to run, application is without power source support；Adopt pH electrode and carbon dioxide electrode, based on Nernst equation, ionic dissociation equilibrium equation and temperature compensation algorithm, set up high-precision quantitative computational algorithm, solve measurement result accuracy problems.
For verifying the reliability of detecting instrument of the present invention and method, we adopt the NaHCO of three kinds of variable concentrations3Solution, uses bipolar electrode method fast detector of the present invention and prior art titrimetry respectively the bicarbonate radical of somewhere, Guizhou and In A Certain Area, qinghai water sample and carbonate content to be carried out quick test experience, and result is as shown in table 1.
Table 1 temperature survey comparing result
Table data in analysis are it can be seen that in the contrast experiment of mark liquid, titrimetry and bipolar electrode method fast detector, the testing result of detecting instrument bicarbonate radical of the present invention is closer to mark liquid value, relative error≤10%.The detection data of detecting instrument of the present invention are closer to indoor titrimetry test data, all within zone of reasonableness.In titrimetry, the content of carbonate is higher than the detection data of instrument, and main cause is the result that the alkaline matter existed in subsoil water helps to consume hydrochloric acid.Detecting instrument of the present invention shows stable in whole use procedure, is suitable for the requirement that water conservancy project ring Field Geology Investigations is quick, portable, instrument is measured in low-power consumption.
The invention have the advantage that
1. the load power source administrative unit configured in detecting instrument of the present invention has a road can convert battery voltage to the low pressure difference linear voltage regulator for circuit voltage volume, therefore use No. 5 lithium batteries of joint to work long hours, make field that the application support without power source be installed, and by the management of load power source administrative unit, it is possible to achieve super low-power consumption runs；
2. the present invention is based on bipolar electrode method, and application pH value electrode and carbon dioxide electrode achieve the quick detection of bicarbonate radical and carbanion in water, and are all corrected bipolar electrode during detection processing；
3. the present invention is based on ionic dissociation equilibrium equation, and pH value electrode and carbon dioxide electrode are provided with temperature intelligent and compensate function, it is ensured that the accuracy of measurement result；Relative error, lower than 10%, is with a wide range of applications.
4. endoprosthetic's interactive unit in instrument of the present invention, possesses the functions such as electrode alignment, measurement result display in real time, and operation is succinct convenient.
Accompanying drawing explanation
Fig. 1 is detecting instrument system principle of compositionality schematic block diagram of the present invention.
Fig. 2 is the circuit diagram of signal condition unit one of the present invention preferred embodiment.
Fig. 3 is carbon dioxide electrode timing carbon dioxide fit correlation curve of the present invention.
Below in conjunction with drawings and the specific embodiments, the present invention is described further.
Detailed description of the invention
Consult shown in Fig. 1, bipolar electrode method of the present invention realizes bicarbonate radical and carbonate rapid detection apparatus in water and mainly includes six major parts: microprocessor unit 1, man-machine interaction unit 2, signal condition unit 3, temperature collecting cell 4, electrode sensor unit 5, load power source administrative unit 6, wherein, the quantitative Analysis algorithm compensated with temperature intelligent in the built-in high accuracy of systematic microprocessor unit 1.
Described load power source administrative unit 6 includes: Battery pack 61, road LDO (low pressure difference linear voltage regulator) 62 and No. three load switches 63,64,65.In embodiment illustrated in fig. 1, one Battery pack 11 selects a joint 4 to save No. 5 aneroid battery, this battery is converted to stable 3.3V supply voltage through low pressure difference linear voltage regulator LDO62, LDO62 output voltage one tunnel directly powers for microprocessor unit 1, and other 3 tunnels are coupled with load switch 63, load switch 64 and load switch 65.Wherein, load switch 63 is responsible for temperature collecting cell 4 and powers, and load switch 64 is responsible for signal condition unit 3 and powers, and load switch 65 is responsible for man-machine interaction unit 2 and powers.According to the principle of on-demand time sharing power supply, the I/O mouth of micro controller unit 1 control folding and switching off load switch 63, load switch 64 and load switch 65 respectively, thus being embodied as unequally loaded intermittent power supply, it is achieved whole system super low-power consumption runs.
Described microprocessor unit 1 can adopt high integration MSP430 processor, is internally integrated the functions such as multi pass acquisition, real-time clock and mass storage, and is built-in with the quantitative Analysis software program compensated with intelligent temperature.Its 12 bit A/D converters carried are for changing the pH electrode signal after signal condition unit and carbon dioxide electrode signal.
Described electrode sensor unit 5 includes pH electrode and electrode interface, and carbon dioxide electrode and electrode interface.In embodiment illustrated in fig. 1, the built-in reference electrode of pH electrode 51；Electrode interface 52 is connected with signal condition unit 3, is responsible for that pH electrode is exported signal and passes to signal condition unit 3.The built-in reference electrode of carbon dioxide electrode 53, includes the filling liquid for buffer solution ionic strength, and a preferred version is to adopt 0.005M sodium bicarbonate filling liquid.Electrode interface 54 is connected with signal condition unit 3, is responsible for that carbon dioxide electrode is exported signal and passes to signal condition unit 3.
Described signal condition unit 3 is divided into two-way, respectively for pH electrode unit and carbon dioxide unit, including impedance matching circuit (31,34), filter circuit (32,35) and voltage lifting circuit (33,36).In embodiment illustrated in fig. 1, pH electrode interface 52 is connected to impedance matching circuit 31, then the filtered circuit 32 of signal, finally being nursed one's health by positive/negative voltage signal by voltage lifting circuit 33 is forward output signal, and 12 bit A/D converters built-in for microprocessor unit 1 are acquired.Carbon dioxide electrode interface 54 is connected to impedance matching circuit 34, then the filtered circuit 35 of signal, and finally being nursed one's health by positive/negative voltage signal by voltage lifting circuit 36 is forward output signal, and 12 bit A/D converters built-in for microprocessor unit 1 are acquired.The electric potential signal that pH electrode exports with carbon dioxide electrode becomes to be available for, by signal condition cells modulate, the signal that the internal A/D convertor circuit of processor gathers.
Fig. 2 illustrates the circuit theory diagrams (only illustrating a road) of signal condition unit one of the present invention preferred embodiment.Owing to pH electrode and carbon dioxide electrode are high impedance internal resistance (>=108Ω), it is desirable to signal conditioning circuit is it is necessary to have sufficiently high input impedance.In order to reduce measurement noise, improving stability of instrument, measuring circuit selects high impedance, low drifting meter specially amplifier INA121, and its internal input impedance is 1012Ω, is fully able to and meets the needs that electrode signal obtains.In figure, INA121 is that one-level is amplified, and main purpose is that the output signal high-fidelity of pH electrode or carbon dioxide electrode is delivered to next stage.Operational amplifier OPA364 coordinates with resistance R25, R28, R31, the positive/negative voltage signal that electrode exports is converted to positive voltage signal, and is nursed one's health in the scope of the built-in ADC12 module license of microprocessor unit MSP430F5438A.
Described temperature collecting cell 4 mainly includes constant current source driving circuit 41, critesistor 42 and filter circuit 43, in embodiment illustrated in fig. 1,12 bit A/D converters that critesistor 42 is connected to microprocessor unit 1 built-in after output signal filtered circuit 43 conditioning after constant-current source 41 drives are acquired.
Described man-machine interaction unit 2 includes keyboard 21 and LCD MODULE 22.In embodiment illustrated in fig. 1, keyboard 21 is connected with the I/O mouth of microprocessor unit 1, is used for being manually entered, and LCD MODULE 22 is connected with the I/O mouth of microprocessor unit 1, for the display of menu.
By the software program of the present invention, also can realize correction pH electrode, carbon dioxide electrode, be automatically obtained the automatic calculating of pH value, free carbon dioxide concentration, bicarbonate radical and carbanion, and possess intelligent temperature compensation function.
nullBipolar electrode method of the present invention realizes bicarbonate radical and carbonate rapid detection apparatus operation principle in water: microprocessor unit 1 is controlled by the keyboard 21 and the LCD MODULE 22 that first pass through in man-machine interaction unit，Complete the correction of pH value electrode and carbon dioxide electrode，PH value electrode 51 is placed in detected solution，By lower keyboard 21，Signal condition unit 3 is powered by the load switch 64 being controlled load power source administrative unit 6 by microprocessor unit 1，Complete the measurement of pH value，Result shows at Liquid Crystal Module 22，With ion regulating agent detected solution pH value adjusted in the scope of 4-5，Carbon dioxide electrode is placed in detected solution，By lower keyboard 21，Signal condition unit 3 is powered by the load switch 63 being controlled load power source administrative unit 6 by microprocessor unit 1，Complete the measurement of pH value，Result shows at Liquid Crystal Module 22，Microprocessor unit 1 controls the load switch 65 of load power source administrative unit 6 simultaneously is that temperature collecting cell 4 power supply carries out temperature acquisition，Temperature results is for the intelligent compensation of pH value and free carbon dioxide concentration result of calculation，Obtain detected solution pH value and free carbon dioxide concentration in measurement after，Automatically the concentration of bicarbonate radical and carbanion is calculated according to ionic dissociation equilibrium equation，Final result displays at the Liquid Crystal Module 22 of man-machine interaction unit 2.
The concrete grammar step that in water of the present invention, bicarbonate radical and carbonate quickly detect is as follows:
1) build above-mentioned bipolar electrode method realize in water bicarbonate radical and carbonate rapid detection apparatus and be applied in Site Detection；
Spot sampling, start described detecting instrument, it is corrected pH electrode (can being adopt or three point calibrations at 2, prior art can realize, this detecting instrument is with self-correcting function), pH electrode after correction is placed in detected solution and records pH value, now can obtain corresponding path electrode data simultaneously----detected solution hydrogen ion concentration H+(the functional realiey conversion being with by detecting instrument self, herein do not repeat)；
2), after recording the pH value of detected solution, with ion regulating agent, the pH value of detected solution is adjusted to about 4-5 (so that bicarbonate radical and carbonate are completely converted into the form of free carbon dioxide)；
3) in carbon dioxide electrode, 0.005M sodium bicarbonate filling liquid is added, for buffer solution ionic strength (changing pH value with the carbon dioxide generation dissociation reaction entered)；And carbon dioxide electrode is corrected: adopt 10-2mol·L-1、10-3mol·L-1With 10-4mol·L-1Carbon dioxide standard solution electrode is carried out bikini correction.Before demarcation, rinsing electrode in deionized water need to be put the electrodes into, until current potential is stable at about-80mV.Timing signal, is sequentially inserted into electrode by concentration order from low to high, measures the potential value of different mark liquid, needs to use deionized water cleaning electrode after often having surveyed a kind of mark liquid.Carbon dioxide electrode after correction is placed the concentration recording free carbon dioxide in detected solution after adjustment；After obtaining the magnitude of voltage of mark liquid, detecting instrument internal processes will utilize method of least square automatically the logarithm of mark liquid value and the magnitude of voltage of correspondence thereof to be fitted to relation mathematic model.Mathematical relationship curve after matching is as shown in Figure 3.
After having demarcated carbon dioxide electrode, the free carbon dioxide concentration C of tested aqueous solution can be recorded by carbon dioxide electrodeT。
Need exist for especially, it should be noted that, the carbon dioxide electrode of different manufacturers is due to the difference of producing principle and technique, baseline potential and three kinds of potential values marking liquid corresponding also differ, above-mentioned carbon dioxide electrode is corrected be only an embodiment, in the present embodiment select electrode be the proud happy CO35 type Carbon dioxide gas-sensing probe in Shanghai.
4) the two-way electrode data of collection is gone forward side by side trip temperature intelligent compensation according to Nernst equation:
The output current potential of pH electrode and carbon dioxide electrode is linear relationship with the logarithm of detected solution pH value and the logarithm of free carbon dioxide concentration, it then follows Nernst equation, and the temperature-compensating formula of pH value electrode slope is:
SPph=0.1984 × TEMP+54.198 (1)
SP in formulaphFor pH electrode slope, temperature value (DEG C) instantly when TEMP is test；The temperature compensation algorithm of carbon dioxide electrode slope is 1.97mV/10 DEG C, and both: temperature often increases by 10 DEG C, slope increases about 1.97, utilizes this relation carbon dioxide electrode slope can be implemented temperature-compensating, to improve the precision measured.
The microprocessor unit of detecting instrument of the present invention is directly built-in with the quantitative Analysis software algorithm program that intelligent temperature compensates, therefore can also be done directly by detecting instrument of the present invention and the two-way electrode data gathered is carried out temperature intelligent compensation according to Nernst equation, obtain detected solution pH value and the result of free carbon dioxide concentration calculating；
5) calculated pH value and free carbon dioxide concentration results are obtained bicarbonate radical and carbon acid ion concentration according to ionic dissociation equilibrium Equation for Calculating:
K in formula1Constant K is understood for one-level1=10-6.352, K2Constant K is understood for one-level2=10-10.329。CTFor the concentration of the free carbon dioxide of detected solution, carbon dioxide electrode in abovementioned steps 3 measure, H+For detected solution hydrogen ion concentration, pH electrode in abovementioned steps 1 measure, can directly obtain bicarbonate ion concentration HCO according to (2) (3)3 -With carbon acid ion concentration CO3 2-, the output of this testing result is shown at man-machine interaction unit.
The foregoing is only presently preferred embodiments of the present invention, present invention protection is not limited merely to this.Any belong within scope based on the equivalent transformation in technical solution of the present invention.
Claims (10)
1. a bipolar electrode method realizes bicarbonate radical and carbonate rapid detection apparatus in water, it is characterised in that including:
One microprocessor unit, its built-in A/D converter, and also it is built-in with the quantitative Analysis of intelligent temperature compensation and the software algorithm program of bicarbonate radical and carbanion quantitative Analysis；
One pH electrode unit, containing the pH electrode of built-in reference electrode, the electric potential signal that the output of this pH electrode is linear with the logarithm of detected solution hydrogen ion activity；
Carbon dioxide electrode unit, containing the carbon dioxide electrode of built-in reference electrode and filling liquid, the electric potential signal that the output of this electrode is linear with the logarithm of detected solution free carbon dioxide concentration；
One signal condition unit, for the scope by built-in for the output signal condition of pH electrode or carbon dioxide electrode to microprocessor unit A/D converter license；This signal condition unit is two-way, respectively for pH electrode unit and carbon dioxide unit；
One temperature collecting cell, it is made up of thermistor (temperature) sensor, constant-current source circuit and low-pass filter circuit；Described thermistor (temperature) sensor output signal after constant-current source circuit drives is connected with low-pass filter circuit；
One man-machine interaction unit, including keyboard and LCD MODULE；Described keyboard is connected with microprocessor unit I/O, is controlled for this bipolar electrode method is realized bicarbonate radical and carbonate rapid detection apparatus in water and arranges；Described LCD MODULE is connected with described microprocessor unit I/O, for display reminding information and testing result；
One load power source administrative unit, can convert battery voltage to the low pressure difference linear voltage regulator (LDO) for circuit voltage volume and No. three load switches including a battery, a road；Wherein, described low pressure difference linear voltage regulator (LDO) is powered to described microprocessor unit, and described No. three load switches control to cut out or open to think that described signal condition unit, temperature collecting cell and man-machine interaction unit provide running voltage by microprocessor unit I/O mouth；
The signal output part of described signal condition unit connects the signals collecting input of microprocessor unit；Outfan in described temperature collecting cell is connected with the signals collecting input of microprocessor unit.
2. bipolar electrode method according to claim 1 realizes bicarbonate radical and carbonate rapid detection apparatus in water, it is characterised in that: described signal condition unit respectively route impedance matching circuit, low-pass filter circuit and voltage lifting circuit composition；Described pH electrode unit is connected with the impedance matching circuit input on a corresponding road respectively with carbon dioxide electrode unit outfan, after the low-pass filtered device of output signal of described impedance matching circuit, the conditioning of described voltage lifting circuit is forward voltage signal.
3. bipolar electrode method according to claim 2 realizes bicarbonate radical and carbonate rapid detection apparatus in water, it is characterised in that: each impedance matching circuit of described signal condition unit adopts high impedance, low drifting meter specially amplifier INA121.
4. bipolar electrode method according to claim 1 realizes bicarbonate radical and carbonate rapid detection apparatus in water, it is characterised in that:
In the software algorithm program of the quantitative Analysis that intelligent temperature built-in in described microprocessor unit compensates, the temperature-compensating formula of the pH value electrode slope of this software algorithm institute foundation is:
SPph=0.1984 × TEMP+54.198 (1)
SP in formulaphFor pH electrode slope, detected solution temperature value (DEG C) instantly when TEMP is test；
The temperature compensation algorithm of the carbon dioxide electrode slope of this software algorithm institute foundation is " 1.97mV/10 DEG C；
In-situ measurement information from pH electrode and carbon dioxide electrode sends microprocessor unit to after the conditioning output of signal condition unit, and the two-way electrode data collected directly is carried out the process of temperature-compensating by this microprocessor unit；
In the software algorithm program of bicarbonate radical built-in in described microprocessor unit and carbanion quantitative Analysis, it then follows ionic dissociation equilibrium equation, computing formula is:
Wherein, K1For primary dissociation equilibrium constant, K1=10-6.352；K2For second dissociation equilibrium constant, K2=10-10.329；The concentration C of free carbon dioxideTWith detected solution hydrogen ion concentration H+By the on-the-spot test of instrument scene directly calculating conversion acquisition.
5. bipolar electrode method according to claim 1 realizes bicarbonate radical and carbonate rapid detection apparatus in water, it is characterised in that: described pH electrode and carbon dioxide electrode all include reference electrode, and reference electrode is silver-silver chloride electrode.
6. bipolar electrode method according to claim 1 realizes bicarbonate radical and carbonate rapid detection apparatus in water, it is characterised in that: it is filled with the filling liquid for buffer solution ionic strength in described carbon dioxide electrode；Being equipped with the program to carbon dioxide electrode correction inside detecting instrument, the carbon dioxide electrode after this correction to program can directly record the free carbon dioxide concentration of detected solution.
7. bipolar electrode method according to claim 1 realizes bicarbonate radical and carbonate rapid detection apparatus in water, it is characterized in that: described microprocessor adopts MSP430 processor, it carries 12 bit A/D converters for changing the signal of the output signal of the pH electrode after signal condition cell processing, carbon dioxide electrode output signal and temperature collecting cell output.
8. bipolar electrode method realizes bicarbonate radical and a carbonate method for quick in water, has any one described bipolar electrode method in claim 1 to 7 and realizes bicarbonate radical and carbonate rapid detection apparatus in water；It is characterized in that including following method step:
1) field investigation and sampling, starts detecting instrument, pH electrode is corrected, and is placed in detected solution by the pH electrode after correction, records the pH value of now detected solution, corresponding acquisition one path electrode data----detected solution hydrogen ion concentration H+；
2) with ion regulating agent, the pH value of detected solution is adjusted to 4～5, adjusted rear detected solution；
3) in carbon dioxide electrode, the filling liquid for buffer solution ionic strength is added, and carbon dioxide electrode is corrected, carbon dioxide electrode after correction is placed after adjustment in detected solution, records after this adjustment the concentration C of free carbon dioxide in detected solutionT；
4) the two-way electrode data H that will obtain+And CTBring ionic dissociation equilibrium equation into:
In formula: K1For primary dissociation equilibrium constant, K1=10-6.352；K2For second dissociation equilibrium constant, K2=10-10.329；Calculate respectively and obtain bicarbonate ion concentration HCO3 -With carbon acid ion concentration CO3 2-；
5) calculated for step 4 testing result is exported, storage, printing or display.
9. bipolar electrode method according to claim 8 realizes bicarbonate radical and carbonate method for quick in water, it is characterised in that: in described step 2, described ion regulating agent adopts 1M citrate buffer solution.
10. bipolar electrode method according to claim 8 realizes bicarbonate radical and carbonate method for quick in water, it is characterised in that the method in described step 3, carbon dioxide electrode being corrected is: adopt 10-2mol·L-1、10-3mol·L-1With 10-4mol·L-1Carbon dioxide standard solution carbon dioxide electrode is carried out bikini correction, before correction, carbon dioxide electrode is put in deionized water and rinses, until current potential is stable at-80mV ± 5mV；Timing, is sequentially inserted into this carbon dioxide electrode by carbon dioxide concentration of standard solution order from low to high, measures the potential value in each standard solution respectively, needs to use deionized water cleaning electrode after often having surveyed a kind of standard solution；After obtaining the magnitude of voltage of standard solution, instrument internal program utilizing method of least square automatically the logarithm of mark liquid value and the magnitude of voltage of correspondence thereof to be fitted to relation mathematic model, carbon dioxide electrode correction is complete.
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