CN102393415B - Device and method for measuring greenhouse crop nitrogen potassium content - Google Patents
Device and method for measuring greenhouse crop nitrogen potassium content Download PDFInfo
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Abstract
The invention discloses a device and a method for measuring greenhouse crop nitrogen potassium contents; the device comprises a greenhouse crop nitrogen potassium measuring electrode which is parallelly and tightly connected by four micro-glass tubes in an axial direction; the four micro-glass tubes are filled with sensitizers and reference filling liquids; upper liquid levels of three sensitizers are respectively filled with corresponding nitrate ion, ammonium ion, potassium ion filling liquids; the four filling liquids are respectively inserted with one end of a corresponding signal line; the other end of each signal line is in parallel electric connection with a multiplexer; the multiplexer is respectively connected with an instrument amplifier and a microprocessor; signal voltages of nitrate ion concentration, ammonium ion concentration, potassium ion concentration are generated respectively between the signal lines of nitrate ions, ammonium ions, potassium ions and the reference signal line; the concentrations of nitrate ions, ammonium ions, potassium ions at the site to be measured are calculated respectively according to a formula; the concentrations of the three ions in a minimal area can be measured simultaneously and rapidly, and the interaction among the three ions is corrected.
Description
Technical field
The invention belongs to manufacturing technology field, greenhouse, particularly relate to a kind of chamber crop nitrogen potassium content measuring method.
Background technology
The hothouse production yield is big, fertilizer requirement is many, soil fertility consumes height, and fertilising mainly out of proportion the and nutritional deficiency symptoms of main nutrient elements such as nitrogen, potassium occur by manual control through regular meeting, directly influence the yield and quality of crop.Some producer is for fear of the generation of nutritional deficiency problem, and excessive nitrogen, the potash fertilizer used not only causes the waste of fertilizer and the pollution of area source of environment, and can cause the reduction of crop quality, even the underproduction.
Traditional crop nutrition diagnosis mode all is based on producer's experience and laboratory conventionally test, diagnosing the rich scarce weak point of nutrition by rule of thumb is to need just to make judgement when apparent in view to symptom, and may cause injury to crop this moment, and some crop is because the excessive or not enough meeting of fertilizer causes irreversible injury; And artificial diagnosis exists subjectivity and individual difference, and mistaken diagnosis takes place easily.Laboratory conventionally test method mainly contains leaf colour atla sheet method, chemical diagnosis, fertilizer window and uses diagnosis and enzymology diagnosis method etc., these traditional means of testing can destroy making deposits yields, influence plant growth, and need expend great amount of manpower and material resources, poor in timeliness at aspects such as sampling, mensuration, data analyses.
It is quick that microelectrode is measured nutrient ions concentration, convenient, China Patent No. is to disclose a kind of nitrate radical ionic selectivity micro-electrode in 200820228434.7, China Patent No. is to disclose a kind of ammonium ion selective composite micro-electrode in 200820228429.6, Yin Xiaoming etc. disclosed a kind of pair in " plant nutrient and fertilizer journal " the 15th the 3rd phase of volume in 2009 and have hindered the concentration that ammonium radical ion selectivity micro-electrode is measured ammonium radical ion in the rice leaf cell, Jia Lijun etc. 2005 disclose a kind of two resistance ion selectivity in " soil journal " the 42nd the 3rd phase of volume and have measured the not concentration of nitrate ion in the balling pakchoi blade cell of live body, the weak point of these schemes is to detect the concentration of ammonium radical ion or nitrate ion single ionic, and make to exist simultaneously in the object different kinds of ions, can bring interference to ion-selective electrode; Nutritional deficiency can cause that plant endotrophic element ion takes place by significant the variation, and influence each other between the nutrient ion concentration obviously, so only detect single ionic concentration, can't eliminate the influence of main interfering ion, can't react the real nutrition condition of crop.
Summary of the invention
The objective of the invention is in order to overcome above-mentioned the deficiencies in the prior art, provide a kind of chamber crop nitrogen potassium content measurement mechanism and based on the nitrogen potassium content measuring method of this device, can measure the concentration of making nitrate ion, ammonium radical ion and the potassium ion of tiny area in the object simultaneously, improve the precision that detects.
The technical scheme that chamber crop nitrogen potassium content measurement mechanism of the present invention adopts is: comprise a chamber crop nitrogen potassium measurement electrode that closely is joined together to form by four little glass tube axially parallel ground, chamber crop nitrogen potassium measurement electrode is drawn into taper, be filled with the nitrate ion sensitive agent respectively in four little glass tubes, the reference internal-filling liquid, ammonium radical ion sensitive agent and potassium ion sensitive agent, liquid level is filled with corresponding nitrate ion internal-filling liquid respectively on three kinds of described sensitive agents, ammonium radical ion internal-filling liquid, the potassium ion internal-filling liquid, be inserted with corresponding nitrate ion signal wire in four kinds of described internal-filling liquids respectively, ammonium radical ion signal wire, one end of potassium ion signal wire, the other end of every described signal wire all stretches out the outer and parallel multiplexer that is electrically connected of little glass tube, multiplexer connects instrument amplifier and microprocessor respectively, microprocessor connects instrument amplifier and analog quantity/digital quantity converter respectively, and analog quantity/digital quantity converter connects reference voltage source.
The technical scheme that chamber crop nitrogen potassium content measuring method of the present invention adopts comprises the steps: A, chamber crop nitrogen potassium measurement electrode awl end is inserted the chamber crop detected part, microprocessor sends signal amplification factor and instructs to instrument amplifier, and sends analog quantity/digital quantity conversion initialization directive and give analog quantity/digital quantity converter; B, microprocessor send channel selecting and instruct to multiplexer, select nitrate ion, ammonium radical ion, potassium ion signalling channel respectively, between nitrate ion, ammonium radical ion, potassium ion signal wire and reference signal line, produce nitrate ion concentration signal voltage, ammonium radical ion concentration signal voltage, potassium concentration signal voltage respectively; Microprocessor starts analog quantity/digital quantity converter simultaneously V1, V2, V3 is carried out analog quantity/digital quantity conversion, and passes to microprocessor; C, microprocessor calculate the concentration of nitrate ion, ammonium radical ion and the potassium ion of detected part respectively according to following formula:
The lg(nitrate ion concentration)=k11 * V1+k12 * V2+k13 * V3+e11+e12+e13;
Lg(ammonium radical ion concentration)=k21 * V1+k22 * V2+k23 * V3+e21+e22+e23;
The lg(potassium concentration)=k31 * V1+k32 * V2+k33 * V3+e31+e32+e33;
K11 is the nitrate ion sensitivity coefficient, k12 is that the ammonium radical ion is to the interference coefficient of nitrate ion, k13 is that potassium ion is to the interference coefficient of nitrate ion, e11 is nitrate ion error term, e12 be the ammonium radical ion to the mushing error item of nitrate ion, e13 is that potassium ion is to the mushing error item of nitrate ion; K21 is that nitrate ion is to the interference coefficient of ammonium radical ion, k22 is ammonium radical ion sensitivity coefficient, k23 is that potassium ion is to the interference coefficient of ammonium radical ion, e21 is that nitrate ion is to the mushing error item of ammonium radical ion, e22 is ammonium radical ion error term, and e23 is that potassium ion is to the mushing error item of ammonium radical ion; K31 is that nitrate ion is to the interference coefficient of potassium ion, k32 be the ammonium radical ion to the interference coefficient of potassium ion, k33 is the potassium ion sensitivity coefficient, e31 is that nitrate ion is to the mushing error item of potassium ion, e32 be the ammonium radical ion to the mushing error item of potassium ion, e33 is potassium ion error term.
The present invention adopts the beneficial effect after the technique scheme to be:
1, can measure the concentration of chamber crop tiny area nitrate ion, ammonium radical ion and potassium ion simultaneously rapidly, and influencing each other between these three kinds of ions revised;
2, three kinds of nutritional labelings are measured simultaneously, can carry out decoupling zero to the antagonism between the nutrients such as crop nitrate ion, ammonium radical ion and potassium ion, provide detection method and instrument for accurately judging the crop alimentary state;
3, can carry out somatometry to crop.
Description of drawings
Fig. 1 is the structural representation of chamber crop nitrogen potassium content measurement mechanism of the present invention;
Among the figure: 1. chamber crop nitrogen potassium measurement electrode; 2. multiplexer; 3. instrument amplifier; 4. analog quantity/digital quantity converter; 5. reference voltage source; 6. microprocessor; 7. pilot lamp; 8. liquid crystal display; 9. keyboard.
Embodiment
As shown in Figure 1, chamber crop nitrogen potassium content measurement mechanism of the present invention comprises a chamber crop nitrogen potassium measurement electrode 1, chamber crop nitrogen potassium measurement electrode 1 closely is joined together to form by four little glass tube axially parallel ground, and the lower end of chamber crop nitrogen potassium measurement electrode 1 is drawn into taper.The inwall that draws four good little glass tubes is all carried out conventional silanization handle, and under 150 ℃ of temperature, toasted 60 minutes～120 minutes continuously.
Wherein first little conic glass end in four little glass tubes charges into the nitrate ion sensitive agent that liquid column length is 0.1mm～1mm, charging into liquid column length then is the nitrate ion internal-filling liquid of 5mm～30mm, and the nitrate ion internal-filling liquid links to each other with nitrate ion sensitive agent liquid level; End with the nitrate ion signal wire inserts in the nitrate ion internal-filling liquid again, and the other end stretches out little glass tube and fixes with fluid sealant at the mouth of pipe.Equally, second little glass tube front portion in four little glass tubes charges into the reference internal-filling liquid that liquid column length is 5mm～31mm, and in the end insertion reference internal-filling liquid with the reference signal line, the other end stretches out little glass tube and fixes with fluid sealant at the mouth of pipe.The 3rd little glass tube tip in four little glass tubes charges into the ammonium radical ion sensitive agent that liquid column length is 0.1mm～1mm, charging into liquid column length then is the ammonium radical ion internal-filling liquid of 5mm～30mm, ammonium radical ion internal-filling liquid links to each other with ammonium radical ion sensitive agent liquid level, end with ammonium radical ion signal wire inserts ammonium radical ion internal-filling liquid again, and the other end stretches out little glass tube and fixes with fluid sealant at the mouth of pipe.The 4th little glass tube tip in four little glass tubes charges into the potassium ion sensitive agent that liquid column length is 0.1mm～1mm, charging into liquid column length then is the potassium ion internal-filling liquid of 5mm～30mm, the potassium ion internal-filling liquid links to each other with potassium ion sensitive agent liquid level, end with the potassium ion signal wire inserts in the potassium ion internal-filling liquid again, and the other end stretches out little glass tube and fixes with fluid sealant at the mouth of pipe.
Wherein, the nitrate ion sensitive agent is the Ammonium ionophore I-cocktail A of Sigma-Aldrich company, ammonium radical ion sensitive agent is the Nitrate ionophore-cocktail A of Sigma-Aldrich company, and the potassium ion sensitive agent is the Sodium ionophore I-cocktail A of Sigma-Aldrich company.Four little glass tubes of four pipes that little glass tube is Hilgenberg company, the nitrate ion internal-filling liquid is the KCl of 50mM and the KNO of 50mM
3Mixed solution; The reference internal-filling liquid is the KCl solution of 200mM; Ammonium radical ion internal-filling liquid is the KCl solution of 50mM; The potassium ion internal-filling liquid is the KCl solution of 50mM; The Ag/AgCl silk that nitrate ion signal wire, reference signal line, ammonium radical ion signal wire and potassium ion signal wire all use purity 99%, diameter to make with conventional electro-plating method as the silver-colored line of 0.3mm, fluid sealant is epoxy resin.
The nitrate ion signal wire that stretches out little glass tube of chamber crop nitrogen potassium measurement electrode 1, the reference signal line, the parallel input end that is electrically connected multiplexer 2 of ammonium radical ion signal wire and potassium ion signal wire, the output terminal of multiplexer 2 connects instrument amplifier 3 and microprocessor 6 respectively, instrument amplifier 3 connects microprocessor 6 and analog quantity/digital quantity converter 4 respectively, it is multiplexer 2, instrument amplifier 3, analog quantity/digital quantity converter 4, microprocessor 6 is electrically connected successively, simultaneously multiplexer 2, instrument amplifier 3, pilot lamp 7, liquid crystal display 8 and keyboard 9 all directly are electrically connected with microprocessor 6; Analog quantity/digital quantity converter 4 also directly connects microprocessor 6 and reference voltage source 5 respectively.Microprocessor 6 also connects indication 7, liquid crystal display 8 and keyboard 9 respectively with different ports.Outside temperature removing chamber's crop nitrogen potassium measurement electrode 1, above-mentioned all elements all can be produced on the circuit board.
When adopting measurement device chamber crop nitrogen potassium content shown in Figure 1, earlier chamber crop nitrogen potassium measurement electrode 1 lower end awl end is inserted the chamber crop detected part, begin to measure instruction by keyboard 9 inputs, microprocessor 6 sends signal amplification factor and instructs to instrument amplifier 3, and sends analog quantity/digital quantity conversion initialization directive and give analog quantity/digital quantity converter 4.
Then, microprocessor 6 sends channel selecting and instructs to multiplexer 2, select the nitrate ion signalling channel, between nitrate ion signal wire and reference signal line, produce nitrate ion concentration signal voltage V1, start 4 pairs of nitrate ion signal voltages of analog quantity/digital quantity converter V1 simultaneously and carry out analog quantity/digital quantity conversion, pilot lamp 7 shows flicker; Analog quantity/digital quantity converter 4 is whenever finished analog quantity/digital quantity conversion and is about to nitrate ion signal electricity V1 and presses and pass to microprocessor 6.
Microprocessor 6 is individual (such as N=3 at the N that obtains program setting, 5,7,31) after the nitrate ion signal voltage V1 data, begin to judge whether signal voltage is stable: earlier up-to-date N signal voltage data are averaged, then up-to-date signal voltage data and the mean value of receiving is compared, if difference greater than programmed values (such as mean value 0.5%, mean value 10%), nitrate ion signal voltage V1 instability then continues the nitrate ion signalling channel is sampled and judged; Otherwise, preserve the mean value of N up-to-date signal voltage data as the reading of the nitrate ion concentration signal voltage V1 of nitrate ion signalling channel.
Equally, microprocessor 6 sends channel selecting and instructs to multiplexer 2, select ammonium radical ion signalling channel, between ammonium radical ion signal wire and reference signal line, produce ammonium radical ion concentration signal voltage V2, adopt the reading that obtains the ammonium radical ion concentration signal voltage V2 of ammonium radical ion signalling channel with the similar step method of above-mentioned selection nitrate ion signalling channel; Microprocessor 6 sends channel selecting and instructs to multiplexer 2, select the potassium ion signalling channel, between potassium ion signal wire and reference signal line, produce potassium concentration signal voltage V3, obtain the reading of the potassium concentration signal voltage V3 of potassium ion signalling channel with the similar step method of above-mentioned selection nitrate ion signalling channel.
At last, microprocessor 6 is according to following formula (1), formula (2) and formula (3), eliminate the influence of interionic phase mutual interference, calculate the concentration of nitrate ion, ammonium radical ion and the potassium ion at the tested position of crop, and in liquid crystal display 8, show, pilot lamp 7 is long bright simultaneously, and expression is measured and finished;
The lg(nitrate ion concentration)=k11 * V1+k12 * V2+k13 * V3+e11+e12+e13 (1)
Wherein k11 is the nitrate ion sensitivity coefficient, k12 is that the ammonium radical ion is to the interference coefficient of nitrate ion, k13 is that potassium ion is to the interference coefficient of nitrate ion, e11 is nitrate ion error term, e12 be the ammonium radical ion to the mushing error item of nitrate ion, e13 is that potassium ion is to the mushing error item of nitrate ion;
Lg(ammonium radical ion concentration)=k21 * V1+k22 * V2+k23 * V3+e21+e22+e23 (2)
Wherein k21 is that nitrate ion is to the interference coefficient of ammonium radical ion, k22 is ammonium radical ion sensitivity coefficient, k23 is that potassium ion is to the interference coefficient of ammonium radical ion, e21 is that nitrate ion is to the mushing error item of ammonium radical ion, e22 is ammonium radical ion error term, and e23 is that potassium ion is to the mushing error item of ammonium radical ion;
The lg(potassium concentration)=k31 * V1+k32 * V2+k33 * V3+e31+e32+e33 (3)
Wherein k31 is that nitrate ion is to the interference coefficient of potassium ion, k32 be the ammonium radical ion to the interference coefficient of potassium ion, k33 is the potassium ion sensitivity coefficient, e31 is that nitrate ion is to the mushing error item of potassium ion, e32 be the ammonium radical ion to the mushing error item of potassium ion, e33 is potassium ion error term.
Before inserting the standard solution of variable concentrations or heterogeneity with chamber crop nitrogen potassium measurement electrode 1, should clean up and dry with the ultrapure water of resistivity greater than 18M Ω cm earlier.After the lower end awl end insertion chamber crop detected part with chamber crop nitrogen potassium measurement electrode, between nitrate ion signal wire and reference signal line, produce nitrate ion concentration signal voltage V1, between ammonium radical ion signal wire and reference signal line, produce ammonium radical ion concentration signal voltage V2, between potassium ion signal wire and reference signal line, produce potassium concentration signal voltage V3, utilize V1, V2 and V3 to calculate each ion concentration respectively:
The lg(nitrate ion concentration)=k11 * V1+k12 * V2+k13 * V3+e11+e12+e13 (1)
Wherein: k11 is the nitrate ion sensitivity coefficient, k12 is that the ammonium radical ion is to the interference coefficient of nitrate ion, k13 is that potassium ion is to the interference coefficient of nitrate ion, e11 is nitrate ion error term, e12 be the ammonium radical ion to the mushing error item of nitrate ion, e13 is that potassium ion is to the mushing error item of nitrate ion;
Lg(ammonium radical ion concentration)=k21 * V1+k22 * V2+k23 * V3+e21+e22+e23 (2)
Wherein: k21 is that nitrate ion is to the interference coefficient of ammonium radical ion, k22 is ammonium radical ion sensitivity coefficient, k23 is that potassium ion is to the interference coefficient of ammonium radical ion, e21 is that nitrate ion is to the mushing error item of ammonium radical ion, e22 is ammonium radical ion error term, and e23 is that potassium ion is to the mushing error item of ammonium radical ion;
The lg(potassium concentration)=k31 * V1+k32 * V2+k33 * V3+e31+e32+e33 (3)
Wherein: k31 is that nitrate ion is to the interference coefficient of potassium ion, k32 is that the ammonium radical ion is to the interference coefficient of potassium ion, k33 is the potassium ion sensitivity coefficient, e31 is that nitrate ion is to the mushing error item of potassium ion, e32 be the ammonium radical ion to the mushing error item of potassium ion, e33 is potassium ion error term.
Definite method of each parameter k11 of nitrate ion electrode part, k12, k13, e11, e12, e13, k11, k21, k22, e21, e22, e23, k31, k32, e31, e32, e33 is as follows in above-mentioned formula (1)-(3): before chamber crop nitrogen potassium measurement electrode 1 is inserted the standard solution of variable concentrations or heterogeneity, should clean up and dry with the ultrapure water of resistivity greater than 18M Ω cm earlier.For nitrate ion potential electrode part, utilize the known nitrate ion standard solution of concentration that k11, k12, k13, e11, e12 and e13 in the formula (1) are demarcated earlier, then formula (1) is changed to:
Lg(nitrate ion concentration of standard solution)=k11 * V1+k12 * V2+k13 * V3+e11+e12+e13 (4)
The chamber crop nitrogen potassium measurement electrode of making 1 is inserted in the nitrate ion standard solution that concentration is 0.01mM, 0.1mM, 1 mM, 10 mM and 100 mM in order successively, after treating that nitrate ion concentration signal voltage V1 is stable, record nitrate ion concentration of standard solution and corresponding V1 value, totally 5 groups of nominal datas.Do not have ammonium radical ion and potassium ion in the solution, can make formula (4) middle k12, k13, e12 and e13 is 0, and then formula (4) is reduced to
Lg(nitrate ion concentration of standard solution)=k11 * V1+e11 (5)
Like this, formula (5) is converted into determines k11 and e11, and with the V1 value substitution formula (5) that measures, different k11 and e11 can obtain different nitrate ion concentration calculated values.Adopting least square method, is principle with the error sum of squares minimum, and namely the nitrate ion concentration calculated value of 5 groups of nominal datas is principle with the quadratic sum minimum of the difference of corresponding nitrate ion concentration of standard solution, calculates k11 and e11.
In the nitrate ion standard solution of 0.01mM, 0.1mM, 1 mM, 10 mM and 100 mM, add the ammonium radical ion, make that ammonium radical ion concentration reaches 0.01mM, 0.1mM, 1 mM, 10 mM and 100 mM in the solution, under every kind of concentration combination, all record nitrate ion concentration, nitrate ion concentration signal voltage V1 value and ammonium radical ion concentration signal voltage V2 value, totally 25 groups of nominal datas one time.Do not have potassium ion in the solution, can make the middle k13 of formula (4) and e13 is 0, and then formula (4) is reduced to
Lg(nitrate ion concentration of standard solution)=k11 * V1+k12 * V2+e11+e12 (6)
Owing to above-mentionedly determined k11 and e11, like this, formula (6) turns to determines k12 and e12.With the V1 value and the V2 value substitution formula (6) that measure, different k12 and e12 can obtain different nitrate ion concentration calculated values.Adopting least square method, is principle with the error sum of squares minimum, and namely the nitrate ion concentration calculated value of 25 groups of nominal datas is principle with the quadratic sum minimum of the difference of corresponding nitrate ion concentration of standard solution, calculates k12 and e12.
In the nitrate ion standard solution of 0.01mM, 0.1mM, 1 mM, 10 mM and 100 mM, add potassium ion, make that potassium concentration reaches 0.01mM, 0.1mM, 1 mM, 10 mM and 100 mM in the solution, under every kind of concentration combination, all record nitrate ion concentration, nitrate ion concentration signal voltage V1 value, ammonium radical ion concentration signal voltage V2 value and potassium concentration signal voltage V3 value one time, totally 25 groups of nominal datas, the fixed k11 of substitution, k12, e11 and e12 are in formula (4), and problem is converted into determining of k13 and e13.With the V1 value, V2 value and the V3 value substitution formula (4) that measure, different k13 and e13 can obtain different nitrate ion concentration calculated values.Adopting least square method, is principle with the error sum of squares minimum, and namely the nitrate ion concentration calculated value of 25 groups of nominal datas is principle with the quadratic sum minimum of the difference of corresponding nitrate ion concentration of standard solution, calculates k13 and e13.
In like manner, definite method of definite method of parameter k21, k22, e21, e22, e23, k31, k32, e31, e32, e33 and above-mentioned k11, k12, k13, e11, e12, e13, k11 is similar, below explains respectively:
Ammonium radical ion potential electrode part utilizes the known ammonium radical ion standard solution of concentration that k21, k22, k23, e21, e22 and e23 in the formula (2) are determined that formula (2) is changed to
Lg(ammonium radical ion concentration of standard solution)=k21 * V1+k22 * V2+k23 * V3+e21+e22+e23 (7)
The chamber crop nitrogen potassium measurement electrode of making 1 is inserted in the ammonium radical ion standard solution that concentration is 0.01mM, 0.1mM, 1 mM, 10 mM and 100 mM in order successively, after treating that ammonium radical ion concentration signal voltage V2 is stable, record ammonium radical ion concentration of standard solution and corresponding V2 value, totally 5 groups of nominal datas.Do not have nitrate ion and potassium ion in the solution, can make formula (7) middle k21, k23, e21 and e23 is 0, and then formula (7) is reduced to
Lg(ammonium radical ion concentration of standard solution)=k22 * V2+e22 (8)
Problem is converted into determines k22 and e22.With the V2 value substitution formula (8) that measures, different k22 and e22 can obtain different ammonium radical ion concentration calculated values.Adopting least square method, is principle with the error sum of squares minimum, and namely the ammonium radical ion concentration calculated value of 5 groups of nominal datas is principle with the quadratic sum minimum of the difference of corresponding ammonium radical ion concentration of standard solution, calculates k22 and e22;
In the ammonium radical ion standard solution of 0.01mM, 0.1mM, 1 mM, 10 mM and 100 mM, add nitrate ion, make that nitrate ion concentration reaches 0.01mM, 0.1mM, 1 mM, 10 mM and 100 mM in the solution, under every kind of concentration combination, all record ammonium radical ion concentration, nitrate ion concentration signal voltage V1 value and ammonium radical ion concentration signal voltage V2 value, totally 25 groups of nominal datas one time.Do not have potassium ion in the solution, can make the middle k23 of formula (7) and e23 is 0, and then formula (7) is reduced to:
Lg(ammonium radical ion concentration of standard solution)=k21 * V1+k22 * V2+e21+e22 (9)
K22 and e22 determine that problem is converted into determines k21 and e21.With V1 value and the V2 value substitution formula (9) that measures, different k21 and e21 can obtain different ammonium radical ion concentration calculated values.Adopting least square method, is principle with the error sum of squares minimum, and namely the ammonium radical ion concentration calculated value of 25 groups of nominal datas is principle with the quadratic sum minimum of the difference of corresponding ammonium radical ion concentration of standard solution, calculates k21 and e21;
In the ammonium radical ion standard solution of 0.01mM, 0.1mM, 1 mM, 10 mM and 100 mM, add potassium ion, make that potassium concentration reaches 0.01mM, 0.1mM, 1 mM, 10 mM and 100 mM in the solution, under every kind of concentration combination, all record ammonium radical ion concentration, nitrate ion concentration signal voltage V1 value, ammonium radical ion concentration signal voltage V2 value and potassium concentration signal voltage V3 value one time, totally 25 groups of nominal datas, the fixed k21 of substitution, k22, e21 and e22 are in formula (7), and problem is converted into determining of k23 and e23.With V1 value, V2 value and the V3 value substitution formula (7) that measures, different k23 and e23 can obtain different ammonium radical ion concentration calculated values.Adopting least square method, is principle with the error sum of squares minimum, and namely the ammonium radical ion concentration calculated value of 25 groups of nominal datas is principle with the quadratic sum minimum of the difference of corresponding ammonium radical ion concentration of standard solution, calculates k23 and e23;
Potassium ion potential electrode part utilizes the known potassium ion standard solution of concentration that k31, k32, k33, e31, e32 and e33 in the formula (3) are determined that formula (3) is changed to
Lg(potassium ion concentration of standard solution)=k31 * V1+k32 * V2+k33 * V3+e31+e32+e33 (10)
The chamber crop nitrogen potassium measurement electrode of making 1 is inserted in the potassium ion standard solution that concentration is 0.01mM, 0.1mM, 1 mM, 10 mM and 100 mM in order successively, after treating that potassium concentration signal voltage V3 is stable, record potassium ion concentration of standard solution and corresponding V3 value, totally 5 groups of nominal datas.Do not have nitrate ion and ammonium radical ion in the solution, can make formula (10) middle k31, k32, e31 and e32 is 0, and then formula (10) is reduced to
Lg(potassium ion concentration of standard solution)=k33 * V3+e33 (11)
Problem is converted into determines k33 and e33.With the potassium concentration signal voltage V3 value substitution formula (11) that measures, different k33 and e33 can obtain different potassium concentration calculated values.Adopting least square method, is principle with the error sum of squares minimum, and namely the potassium concentration calculated value of 5 groups of nominal datas is principle with the quadratic sum minimum of the difference of corresponding potassium ion concentration of standard solution, calculates k33 and e33;
In the potassium ion standard solution of 0.01mM, 0.1mM, 1 mM, 10 mM and 100 mM, add nitrate ion, make that nitrate ion concentration reaches 0.01mM, 0.1mM, 1 mM, 10 mM and 100 mM in the solution, under every kind of concentration combination, all record potassium concentration, nitrate ion concentration signal voltage V1 value and potassium concentration signal voltage V3 value, totally 25 groups of nominal datas one time.Do not have the ammonium radical ion in the solution, can make the middle k32 of formula (10) and e32 is 0, and then formula (10) is reduced to
Lg(potassium ion concentration of standard solution)=k31 * V1+k33 * V3+e31+e33 (12)
K33 and e33 determine that problem is converted into determines k31 and e31.With the V1 value and the V3 value substitution formula (12) that measure, different k31 and e31 can obtain different potassium concentration calculated values.Adopting least square method, is principle with the error sum of squares minimum, and namely the potassium concentration calculated value of 25 groups of nominal datas is principle with the quadratic sum minimum of the difference of corresponding potassium ion concentration of standard solution, calculates k31 and e31;
In the potassium ion standard solution of 0.01mM, 0.1mM, 1 mM, 10 mM and 100 mM, add the ammonium radical ion, make that ammonium radical ion concentration reaches 0.01mM, 0.1mM, 1 mM, 10 mM and 100 mM in the solution, under every kind of concentration combination, all record potassium concentration, nitrate ion concentration signal voltage V1 value, ammonium radical ion concentration signal voltage V2 value and potassium concentration signal voltage V3 value one time, totally 25 groups of nominal datas, the fixed k31 of substitution, k33, e31 and e33 are in formula (10), and problem is converted into determining of k32 and e32.The acquired k31 of substitution, k33, e31 and e33, with the V1 value, V2 value and the V3 value substitution formula (10) that measure, different k32 and e32 can obtain different potassium concentration calculated values.Adopting least square method, is principle with the error sum of squares minimum, and namely the potassium concentration calculated value of 25 groups of nominal datas is principle with the quadratic sum minimum of the difference of corresponding potassium ion concentration of standard solution, calculates k32 and e32.
Claims (3)
1. chamber crop nitrogen potassium content measuring method, adopt chamber crop nitrogen potassium content measurement mechanism, described chamber crop nitrogen potassium content measurement mechanism comprises a chamber crop nitrogen potassium measurement electrode (1) that closely is joined together to form by four little glass tube axially parallel ground, chamber crop nitrogen potassium measurement electrode (1) is drawn into taper, be filled with the nitrate ion sensitive agent respectively in four little glass tubes, the reference internal-filling liquid, ammonium radical ion sensitive agent and potassium ion sensitive agent, liquid level is filled with corresponding nitrate ion internal-filling liquid respectively on three kinds of described sensitive agents, ammonium radical ion internal-filling liquid, the potassium ion internal-filling liquid, be inserted with corresponding nitrate ion signal wire in four kinds of described internal-filling liquids respectively, the reference signal line, ammonium radical ion signal wire, one end of potassium ion signal wire, the other end of every described signal wire all stretches out the outer and parallel multiplexer (2) that is electrically connected of little glass tube, multiplexer (2) connects instrument amplifier (3) and microprocessor (6) respectively, microprocessor (6) connects instrument amplifier (3) and analog quantity/digital quantity converter (4) respectively, analog quantity/digital quantity converter (4) connects reference voltage source (5), it is characterized in that comprising the steps:
A, chamber crop nitrogen potassium measurement electrode (1) awl end is inserted the chamber crop detected part, microprocessor (6) sends signal amplification factor and instructs to instrument amplifier (3), and sends analog quantity/digital quantity conversion initialization directive and give analog quantity/digital quantity converter (4);
B, microprocessor (6) send channel selecting and instruct to multiplexer (2), select nitrate ion, ammonium radical ion, potassium ion signalling channel respectively, between nitrate ion, ammonium radical ion, potassium ion signal wire and reference signal line, produce nitrate ion concentration signal voltage V1, ammonium radical ion concentration signal voltage V2, potassium concentration signal voltage V3 respectively; Microprocessor (6) starts analog quantity/digital quantity converter (4) simultaneously V1, V2, V3 is carried out analog quantity/digital quantity conversion, and passes to microprocessor (6);
C, microprocessor (6) calculate the concentration of nitrate ion, ammonium radical ion and the potassium ion of detected part respectively according to following formula:
The lg(nitrate ion concentration)=k11 * V1+k12 * V2+k13 * V3+e11+e12+e13 (1)
Lg(ammonium radical ion concentration)=k21 * V1+k22 * V2+k23 * V3+e21+e22+e23 (2)
The lg(potassium concentration)=k31 * V1+k32 * V2+k33 * V3+e31+e32+e33 (3)
K11 is the nitrate ion sensitivity coefficient, k12 is that the ammonium radical ion is to the interference coefficient of nitrate ion, k13 is that potassium ion is to the interference coefficient of nitrate ion, e11 is nitrate ion error term, e12 be the ammonium radical ion to the mushing error item of nitrate ion, e13 is that potassium ion is to the mushing error item of nitrate ion; K21 is that nitrate ion is to the interference coefficient of ammonium radical ion, k22 is ammonium radical ion sensitivity coefficient, k23 is that potassium ion is to the interference coefficient of ammonium radical ion, e21 is that nitrate ion is to the mushing error item of ammonium radical ion, e22 is ammonium radical ion error term, and e23 is that potassium ion is to the mushing error item of ammonium radical ion; K31 is that nitrate ion is to the interference coefficient of potassium ion, k32 be the ammonium radical ion to the interference coefficient of potassium ion, k33 is the potassium ion sensitivity coefficient, e31 is that nitrate ion is to the mushing error item of potassium ion, e32 be the ammonium radical ion to the mushing error item of potassium ion, e33 is potassium ion error term.
2. method according to claim 1, it is characterized in that: among the step B, microprocessor (6) is averaged N=3 to up-to-date N ion concentration signal voltage data earlier, 5,7 ..., 31, then up-to-date ion concentration signal voltage data and the mean value of receiving is compared, if difference is greater than setting value, signal voltage instability then continues signalling channel is sampled and judged; Otherwise, preserve the mean value of N up-to-date ion concentration signal voltage data as V1, V2, V3.
3. method according to claim 1, it is characterized in that: definite method of the k11 described in the step C, k12, k13, e11, e12, e13 is: utilize the known nitrate ion standard solution of concentration that k11, k12, k13, e11, e12 and e13 in the formula (1) are demarcated earlier, then formula (1) is changed to:
Lg(nitrate ion concentration of standard solution)=k11 * V1+k12 * V2+k13 * V3+e11+e12+e13 (4)
Chamber crop nitrogen potassium measurement electrode (1) is inserted in the nitrate ion standard solution that concentration is 0.01mM, 0.1mM, 1 mM, 10 mM and 100 mM in order successively, record 5 groups of nitrate ion concentration of standard solution and corresponding nitrate ion concentration signal voltage V1, there are not ammonium radical ion and potassium ion in the solution, making formula (4) middle k12, k13, e12 and e13 is 0, and then formula (4) is reduced to:
Lg(nitrate ion concentration of standard solution)=k11 * V1+e11 (5)
With V1 value substitution formula (5), obtain different nitrate ion concentration calculated values, adopt least square method to calculate k11 and e11;
In the nitrate ion standard solution of 0.01mM, 0.1mM, 1 mM, 10 mM and 100 mM, add the ammonium radical ion, make that ammonium radical ion concentration reaches 0.01mM, 0.1mM, 1 mM, 10 mM and 100 mM in the solution, under every kind of concentration combination, all record nitrate ion concentration, nitrate ion concentration signal voltage V1 value and ammonium radical ion concentration signal voltage V2 value one time, there is not potassium ion in the solution, make that k13 and e13 are 0, then formula (4) is reduced to:
Lg(nitrate ion concentration of standard solution)=k11 * V1+k12 * V2+e11+e12 (6)
V1 value and V2 value substitution formula (6) with measuring obtain different nitrate ion concentration calculated values, adopt least square method to calculate k12 and e12;
At 0.01mM, 0.1mM, 1 mM, add potassium ion in the nitrate ion standard solution of 10 mM and 100 mM, make that potassium concentration reaches 0.01mM in the solution, 0.1mM, 1 mM, 10 mM and 100 mM, under every kind of concentration combination, all record nitrate ion concentration one time, nitrate ion concentration signal voltage V1 value, ammonium radical ion concentration signal voltage V2 value and potassium concentration signal voltage V3 value, the fixed k11 of substitution, k12, e11 and e12 are in formula (4), obtain different nitrate ion concentration calculated values, adopt least square method to calculate k13 and e13.
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