CN112540110A - Method for measuring calcium content in feed by using ion selective electrode - Google Patents
Method for measuring calcium content in feed by using ion selective electrode Download PDFInfo
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000011575 calcium Substances 0.000 title claims abstract description 41
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 33
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 143
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 141
- 239000012488 sample solution Substances 0.000 claims abstract description 112
- 239000011159 matrix material Substances 0.000 claims abstract description 86
- 239000000523 sample Substances 0.000 claims abstract description 84
- 239000000243 solution Substances 0.000 claims abstract description 61
- 150000002500 ions Chemical class 0.000 claims abstract description 40
- 239000012086 standard solution Substances 0.000 claims abstract description 33
- 238000001514 detection method Methods 0.000 claims abstract description 26
- 238000000605 extraction Methods 0.000 claims abstract description 26
- 238000012546 transfer Methods 0.000 claims description 61
- 238000012937 correction Methods 0.000 claims description 39
- 238000005070 sampling Methods 0.000 claims description 38
- 239000007788 liquid Substances 0.000 claims description 34
- 239000013582 standard series solution Substances 0.000 claims description 28
- 238000010521 absorption reaction Methods 0.000 claims description 27
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 22
- 238000005259 measurement Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000007865 diluting Methods 0.000 claims description 16
- 238000002347 injection Methods 0.000 claims description 13
- 239000007924 injection Substances 0.000 claims description 13
- 239000001110 calcium chloride Substances 0.000 claims description 8
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 102000004169 proteins and genes Human genes 0.000 claims description 3
- 108090000623 proteins and genes Proteins 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 238000012360 testing method Methods 0.000 claims description 3
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 241001465754 Metazoa Species 0.000 description 6
- 238000004448 titration Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 3
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000004380 ashing Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000021321 essential mineral Nutrition 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 238000001637 plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/333—Ion-selective electrodes or membranes
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/4163—Systems checking the operation of, or calibrating, the measuring apparatus
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- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
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Abstract
The invention relates to a method for measuring calcium content in feed by using an ion selective electrode, which comprises the steps of preparing standard solution, measuring the potential value of the standard solution, generating standard curve and function, preparing sample solution to be detected, detecting the potential value of the solution to be detected, extracting calcium ions in the sample solution, detecting the potential value of the extracted sample solution to judge the amount of interference ions, calculating the calcium ion content in the solution and calculating the calcium content in the sample. A blank potential value numerical matrix and a compensation parameter calculation parameter matrix of the blank potential value to the measured potential value are arranged in the central control system, blank detection is carried out before a standard solution is detected, the measured potential value is compensated according to a detection result, blank influence is removed, and detection accuracy is improved; calcium ions in the sample extraction solution to be detected are detected, the potential value of the extracted sample solution is detected, the influence of the calcium ions and substances in the sample solution is removed, and the detection accuracy is further improved.
Description
Technical Field
The invention relates to the technical field of ion detection, in particular to a method for determining calcium content in feed by using an ion selective electrode.
Background
Calcium is an inorganic salt which is the most abundant in the animal body and is called as a 'life element', and the calcium in the animal body can form bones and teeth on one hand and participate in various physiological functions and metabolic processes on the other hand to influence the activities of various organ tissues. Excessive intake of calcium can affect the absorption rate of animals on other essential minerals such as iron, zinc and the like, and can cause related diseases, the lack of calcium can cause physiological disorder of the animals, and further cause a series of serious diseases, and the animals mainly obtain the required calcium through feeds, so that the rapid and accurate determination of the calcium content in the feeds and raw materials is of great importance to feed enterprises.
The method for measuring calcium element adopted by the feed industry at present mainly comprises a chemical titration method, an atomic absorption spectrometry, a plasma emission spectrometry, an ion chromatography and the like, and the method for measuring calcium in the feed issued by the nation comprises the chemical titration method and the atomic absorption spectrometry.
The existing national standard detection method for calcium element in feed is GB/T6436-2018 determination of calcium in feed and GB/T13885 & 2017 determination of calcium, copper, iron, magnesium, manganese, potassium, sodium and zinc content in feed by atomic absorption spectrometry, the international more general European method is EN 15510 & 2017 sampling and ICP-AES method for calcium, sodium, phosphorus, magnesium, potassium, iron, zinc, copper, manganese, cobalt, molybdenum and lead determination in animal feed, the detection method using the instrument has the defects of expensive instrument consumables, more complicated operation, long time consumption and the like, and the conventional titration method has the defects of complicated steps, long time consumption, easiness in interference, difficulty in end point determination and the like.
Disclosure of Invention
Therefore, the invention provides a method for measuring the content of calcium in feed by using an ion selective electrode, which is used for overcoming the problems of complex steps and long time consumption of the calcium ion detection process in the prior art.
In order to achieve the above object, the present invention provides a method for determining calcium content in feed by using an ion selective electrode, comprising:
s1, preparing 0.1mol/L standard calcium chloride solution, accurately transferring a specified amount of standard calcium chloride solution, and diluting to obtain various calcium chloride solutions with specific concentrations;
s2, potential values of calcium chloride solutions with different specific concentrations are determined through a primary battery test, and the potential values and the concentration values are input into a central control system of the values to generate a standard curve and a function corresponding to the standard curve;
s3, melting and diluting the sample to be detected, and detecting the potential value of the sample solution;
s4, removing calcium ions in the sample to be detected, detecting the potential value of the sample solution after the extraction of the calcium ions, and judging whether interference ions exist or not;
and S5, revising the potential value, calculating the content of calcium ions in the solution according to the revised potential value and the standard curve, and calculating the content of calcium in the sample according to the content of calcium ions.
Furthermore, a central control system is arranged in the process of adopting the method for measuring the calcium content in the feed by utilizing the ion selective electrode; the central control system is provided with a standard calcium chloride solution transfer amount matrix A0, the transfer amounts arranged in the matrix A0 are sequentially and accurately transferred to different beakers, calcium ion standard series solutions with different concentrations are obtained by diluting with water, and a calcium ion standard series solution concentration matrix G0 is generated;
a blank potential value numerical value matrix E0 and a compensation parameter calculation parameter matrix BO of the blank potential value to the measured potential value are arranged in the central control system; measuring a blank potential value E and transmitting a detection result to the central control system, wherein the central control system calculates a compensation parameter C of the blank potential value to the measured potential value according to the E; detecting calcium ion standard series solutions with different concentrations in sequence to obtain measured values of each standard solution, generating a standard series solution measured value matrix a0 by a central control system, compensating the measured values in the matrix a0 according to a compensation parameter C by the central control system, calculating potential correction values ej of the solutions with different concentrations, sequentially calculating the measured values in the matrix a0 by the central control system and generating a potential correction value matrix e0, and generating a standard curve and a function corresponding to the standard curve by the central control system according to e 0;
and (3) diluting the sample to be detected with the mass M, filtering the sample to be detected into a sample solution, dissolving the sample, detecting the potential value a of the sample solution, transmitting the detection result to a central control system, and comparing the internal parameters a and a0 by the central control system to adjust the sampling quality.
Further, when a is in a preset range, pouring another sample into the calcium ion absorption device to extract calcium ions in the solution; detecting the potential value az of the extracted calcium ion sample solution; the central control system calculates the potential value ratio H of the sample solution after the extraction of the calcium ions and the sample solution before the extraction of the calcium ions, compares H with a potential difference ratio parameter H, judges whether interference ions exist in the sample solution or not, judges more interference ions exist in the sample solution, corrects the potential value of the sample solution before the extraction of the calcium ions, calculates a potential correction value ex of the sample solution according to a correction value, brings the ex into a function corresponding to the standard curve to obtain the concentration Gx of the calcium ions in the sample solution, and calculates the content X of the calcium in the sample according to the Gx.
Weighing 1.11g of calcium chloride reagent which is burned at 550 ℃ for 1h and cooled, placing the reagent in a beaker, adding water to dissolve the reagent, transferring the reagent into a volumetric flask with 100mL, diluting the reagent to a scale with water, shaking up the reagent to prepare a standard calcium chloride solution with 0.1mol/L, wherein the content of calcium ions in the solution is 4 mg/mL;
the central control system is provided with a standard calcium chloride solution transfer amount matrix A0 (A1, A2, A3, A4, A5 and A6), wherein A1 is a first preset transfer amount, A2 is a second preset transfer amount, A3 is a third preset transfer amount, A4 is a fourth preset transfer amount, A5 is a fifth preset transfer amount, A6 is a sixth preset transfer amount, and the values of the transfer amounts are sequentially increased;
transferring the transfer amounts arranged in the matrix A0 to different beakers in sequence and accurately, adding pure water to dissolve the calcium ions, transferring the calcium ions to 50mL volumetric flasks respectively after the calcium ions are dissolved, diluting the calcium ions to scales by using water to obtain calcium ion standard series solutions with different concentrations, generating a calcium ion standard series solution concentration matrix G0 (G1, G2, G3, G4, G5 and G6) by a central control system, wherein G1 corresponds to the solution concentration of a first preset transfer amount, G2 corresponds to the solution concentration of a second preset transfer amount, G3 corresponds to the solution concentration of a third preset transfer amount, G4 corresponds to the solution concentration of a fourth preset transfer amount, G5 corresponds to the solution concentration of a fifth preset transfer amount, and G6 corresponds to the solution concentration of a sixth preset transfer amount.
Further, correctly connecting the calcium ion selective electrode and the saturated calomel electrode with an acidimeter, inserting the electrodes into a plastic beaker filled with 50mL of water, preheating an instrument, stirring at a constant speed on a magnetic stirrer, measuring the potential after the potential is stable, recording a potential value E under a blank condition and transmitting a detection result to a central control system;
a blank potential value numerical value matrix E0 and a compensation parameter calculation parameter matrix BO of the blank potential value to the measured potential value are arranged in the central control system;
for the blank potential value matrices E0, E0(E1, E2, E3, E4), where E1 is a first preset number of blank potential values, E2 is a second preset number of blank potential values, E3 is a third preset number of blank potential values, E4 is a fourth preset number of blank potential values, each of said values increasing in order;
calculating a parameter matrix BO, B0(B1, B2, B3, B4) for a compensation parameter of a blank potential value to a measured potential value, wherein B1 is a compensation parameter calculation parameter of a first preset blank potential value to a measured potential value, B2 is a compensation parameter calculation parameter of a second preset blank potential value to a measured potential value, B3 is a compensation parameter calculation parameter of a third preset blank potential value to a measured potential value, and B4 is a compensation parameter calculation parameter of a fourth preset blank potential value to a measured potential value;
the central control system compares the internal parameters of E and E0:
when E is less than or equal to E1, the central control system does not compensate and calculate the measured potential value according to the blank potential value;
when E is more than E1 and less than or equal to E2, the central control system selects B1 from the B0 matrix as a compensation parameter calculation parameter of the blank potential value to the measured potential value;
when E is more than E2 and less than or equal to E3, the central control system selects B2 from the B0 matrix as a compensation parameter calculation parameter of the blank potential value to the measured potential value;
when E is more than E3 and less than or equal to E4, the central control system selects B3 from the B0 matrix as a compensation parameter calculation parameter of the blank potential value to the measured potential value;
when E is larger than E4, the central control system selects B4 from the B0 matrix as a compensation parameter calculation parameter of the blank potential value to the measured potential value;
when the measured potential value needs to be compensated, the central control system calculates a compensation parameter C, C = (E-E1). times.Bi, i =1,2,3,4 of the blank potential value to the measured potential value.
Further, calcium ion standard series solutions with different concentrations are detected in sequence to obtain measured values of each standard solution, each measured value is input into a central control system, and the central control system generates a standard series solution measured value matrix a0 (a1, a2, A3, a4, a5 and A6), wherein a1 is a measured value of a1 transfer amount standard solution, a2 is a measured value of a2 transfer amount standard solution, A3 is a measured value of A3 transfer amount standard solution, a4 is a measured value of a4 transfer amount standard solution, a5 is a5 transfer amount standard solution, and A6 is a measured value of A6 transfer amount standard solution;
the central control system performs compensation on each measured value in the matrix a0 according to a compensation parameter C, and calculates potential compensation values ej, j =1,2,3,4,5,6, ej = aj-aj × C of each concentration solution;
the central control system calculates the measurement values in the matrix a0 in sequence and generates a potential correction value matrix e0(e1, e2, e3, e4, e5 and e 6);
further, the central control system generates a calcium ion concentration and potential correction value standard curve and generates a function formula G = f (e) corresponding to the curve according to the potential correction value matrix e0 and the calcium ion standard series solution concentration matrix G0, wherein e belongs to [ e1, eg ].
Furthermore, the central control system is further provided with a sample sampling quality compensation parameter matrix N0 (N1, N2), wherein N1 is a sample sampling quality compensation parameter with too low potential value, and N2 is a sample sampling quality compensation parameter with high and low potential value.
Putting a sample to be detected with the mass M into an iodometry bottle, adding 100mL of 1mol/L hydrochloric acid into the iodometry bottle, putting a stirrer into the iodometry bottle, and stirring on a magnetic stirrer for T1; after stirring, putting a proper amount of solution into a 50mL centrifuge tube, and centrifuging for T2 time in a centrifuge at the rotating speed of 4000 r/min; after centrifugation, respectively taking 10mL of supernatant in two beakers, respectively adding a proper amount of ultrapure water into each beaker, adjusting the pH to 7.5 by using a 50% triethanolamine solution, respectively adding 4mL of 1mol/L KCl solution into each beaker after the pH value of the solution is stable, respectively transferring the solution into two 50mL volumetric flasks, and metering to the scale with water.
Further, pouring a sample solution into the plastic beaker, detecting the potential value a of the sample solution and transmitting the detection result to a central control system, wherein the central control system compares the internal parameters a with a 0:
when a is greater than or equal to a1 and less than a6, the central control system judges that the potential value is in a reasonable measurement range and does not adjust the sampling quality of the sample;
when a is not in the range of a1-a 6, the central control system judges that the potential value is not in the reasonable measurement range, and adjusts the sampling quality of the sample;
when a is less than a1, the central control system selects N1 from the matrix N0 as a sample sampling quality compensation parameter, and calculates a sample sampling quality correction value M ', M' = (a 1-a). times.N 1/a 1;
when a is larger than or equal to a6, the central control system selects N2 from the matrix N0 as a sample sampling quality compensation parameter, and the central control system calculates a sample sampling quality correction value M ', M' = a6 multiplied by N2 divided by (a-a 6).
Further, when the central control system corrects the sampling quality of the sample to M ', repeating the sample dissolving operation and detecting the potential value a ' of the sample solution when the sampling quality is M ', wherein the central control system compares the a ' with the internal parameters of a0, and when a1 is more than or equal to a ' < a6, the central control system judges that the potential value does not adjust the sampling quality of the sample within a reasonable measurement range; when a is not in the range of a1-a 6, repeating the sample quality correction operation until a1 is not more than or equal to a' < a 6;
when a is more than or equal to a1 and less than a6, pouring the other sample into a calcium ion absorption device to extract calcium ions in the solution.
Further, the calcium ion absorbing device is connected with the central control system, and comprises: the device comprises a calcium ion absorption net, a liquid injection port plug, a first circulating machine, a second circulating machine, a circulating channel, a first valve, a second valve and a liquid storage bin, wherein the liquid storage bin is used for storing a sample solution to be separated; the calcium ion absorption net is positioned in the liquid storage bin and divides the liquid storage bin into two parts, and a protein carrier capable of absorbing calcium ions is arranged on the calcium ion absorption net; the liquid injection port is positioned at the top of the calcium ion absorption device and is used for injecting a sample solution to be separated into the liquid storage bin; the liquid injection port plug is positioned at the upper part of the liquid injection port, so that liquid splashing is prevented when the sample solution circulates; the first circulating machine is positioned at the initial end of the circulating channel, the second circulating machine is positioned at the tail end of the circulating channel, and each circulating machine is used for circulating the sample solution to be separated in the liquid storage bin; the first valve is connected with the external interface and used for sucking and discharging the sample solution completely by calcium ions; the second valve is arranged on the circulating channel.
Further, when calcium ions are extracted from the sample solution, the central control system starts the first circulating machine and the second circulating machine, closes the first valve and opens the second valve, and the sample solution circulates in the calcium ion absorption device under the action of each circulating machine, wherein the circulating time is T3, T3= (a-a 1). times.alpha + T, wherein alpha is a potential value of the sample solution and a compensation parameter of the circulating time, and T is a basic value of the circulating time.
Furthermore, the central control system is also provided with a potential difference ratio parameter H;
when the circulation time of the sample solution in the calcium ion absorption device reaches T3, the central control system controls the second circulator to stop working, opens the first valve and closes the second valve, the sample solution is discharged into a plastic beaker, and the potential value az of the extracted calcium ion sample solution is detected; the central control system calculates the potential value ratio H, H = az ÷ a of the sample solution after the extraction of the calcium ions and the sample solution before the extraction of the calcium ions, and compares H with H:
when H is less than H, the central control system judges that interference ions in the sample solution are less and does not correct the potential value of the sample solution before calcium ion extraction;
when H is larger than or equal to H, the central control system judges that the number of interference ions in the sample solution is large, the potential value of the sample solution before calcium ion extraction is corrected, the corrected sample value is ax, ax = (a-az) ÷ Z, and Z is a correction parameter of the potential value of the interference ions;
the central control system calculates the potential correction value ex of the sample solution, when H is less than H, ex = a-a × C, and when H is more than or equal to H, ex = ax-ax × C.
Further, the central control system brings the potential correction value ex of the sample solution into a curve function formula G = f (e), e belongs to [ e1, eg ], and the concentration Gx of calcium ions in the sample solution is calculated;
the central control system calculates the content X of calcium in the sample through the concentration Gx of calcium ions in the sample:
X= Gx×K÷1000÷M’×100％
and K is a compensation parameter of the dilution multiple to the calcium ion concentration of the sample.
Compared with the prior art, the invention has the advantages that in the detection process by adopting the method for determining the calcium content in the feed by utilizing the ion selective electrode, compared with a large instrument used in a standard method and the cost of high-purity gas used for detection, the method has low cost of used equipment and consumables and small consumption, and the national standard and European standard methods for detecting the feed, especially the mixed batch, generally need to perform machine or titration detection after ashing and corresponding treatment of the feed, the whole process from sample weighing to result obtaining requires at least about 6-8 hours, the detection result can be obtained generally in the next day, the method can avoid the steps of ashing and the like, realizes that the results from sample weighing to result discharging are finished in about 1 hour, obviously improves the efficiency, and can be used for on-site detection and monitoring of a feed factory due to simple steps and short time, thereby effectively ensuring the product quality and improving the inventory turnover rate; the operation steps are simple and clear, and the operation can be quickly finished.
Further, a blank potential value numerical value matrix E0 and a compensation parameter calculation parameter matrix BO of blank potential values to the measured potential values are arranged in the central control system.
Furthermore, calcium ions in the sample extraction solution to be detected detect the potential value of the extracted sample solution, the influence of the calcium ions and substances in the sample solution is removed, and the detection accuracy is further improved.
Drawings
FIG. 1 is a schematic structural view of a calcium ion absorption device according to the present invention;
FIG. 2 is a schematic flow chart of the method for measuring the calcium content in the feed by using the ion selective electrode according to the invention.
Detailed Description
In order that the objects and advantages of the invention will be more clearly understood, the invention is further described below with reference to examples; it should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Preferred embodiments of the present invention are described below with reference to the accompanying drawings. It should be understood by those skilled in the art that these embodiments are only for explaining the technical principle of the present invention, and do not limit the scope of the present invention.
It should be noted that in the description of the present invention, the terms of direction or positional relationship indicated by the terms "upper", "lower", "left", "right", "inner", "outer", etc. are based on the directions or positional relationships shown in the drawings, which are only for convenience of description, and do not indicate or imply that the device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention.
Furthermore, it should be noted that, in the description of the present invention, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
Fig. 1 is a schematic structural view of a calcium ion absorption device according to the present invention; the calcium ion absorbing device 2 is connected with the central control system 1, and the calcium ion absorbing device 2 comprises: the device comprises a calcium ion absorption net 21, a liquid injection port 22, a liquid injection port plug 23, a first circulating machine 24, a second circulating machine 25, a circulating channel 26, a first valve 27, a second valve 28 and a liquid storage bin 29, wherein the liquid storage bin 29 is used for storing a sample solution to be separated; the calcium ion absorption net 21 is positioned in the liquid storage bin 29 and divides the liquid storage bin 29 into two parts, and a protein carrier capable of absorbing calcium ions is arranged on the calcium ion absorption net 21; the liquid injection port 22 is positioned at the top of the calcium ion absorption device 2 and is used for injecting a sample solution to be separated into the liquid storage bin 29; the liquid injection port plug 23 is positioned at the upper part of the liquid injection port 22, so that liquid splashing is prevented when the sample solution circulates; the first circulator 24 is positioned at the initial end of the circulating channel 26, the second circulator 25 is positioned at the tail end of the circulating channel 26, and each circulator is used for circulating the sample solution to be separated in the liquid storage bin; the first valve 27 is connected with an external interface and is used for sucking and discharging the sample solution completely sucked by calcium ions; the second valve 28 is provided on the circulation passage.
Referring to fig. 2, a schematic flow chart of a method for determining calcium content in feed by using an ion selective electrode according to the present invention is shown, wherein the method for determining calcium content in feed by using an ion selective electrode according to the present invention comprises:
s1, preparing 0.1mol/L standard calcium chloride solution, accurately transferring a specified amount of standard calcium chloride solution, and diluting to obtain various calcium chloride solutions with specific concentrations;
s2, potential values of calcium chloride solutions with different specific concentrations are determined through a primary battery test, and the potential values and the concentration values are input into a central control system of the values to generate a standard curve and a function corresponding to the standard curve;
s3, melting and diluting the sample to be detected, and detecting the potential value of the sample solution;
s4, removing calcium ions in the sample to be detected, detecting the potential value of the sample solution after the extraction of the calcium ions, and judging whether interference ions exist or not;
and S5, revising the potential value, calculating the content of calcium ions in the solution according to the revised potential value and the standard curve, and calculating the content of calcium in the sample according to the content of calcium ions.
Specifically, a central control system is arranged in the process of adopting the method for measuring the calcium content in the feed by utilizing the ion selective electrode; the central control system is provided with a standard calcium chloride solution transfer amount matrix A0, the transfer amounts arranged in the matrix A0 are sequentially and accurately transferred to different beakers, calcium ion standard series solutions with different concentrations are obtained by diluting with water, and a calcium ion standard series solution concentration matrix G0 is generated;
a blank potential value numerical value matrix E0 and a compensation parameter calculation parameter matrix BO of the blank potential value to the measured potential value are arranged in the central control system; measuring a blank potential value E and transmitting a detection result to the central control system, wherein the central control system calculates a compensation parameter C of the blank potential value to the measured potential value according to the E; detecting calcium ion standard series solutions with different concentrations in sequence to obtain measured values of each standard solution, generating a standard series solution measured value matrix a0 by a central control system, compensating the measured values in the matrix a0 according to a compensation parameter C by the central control system, calculating potential correction values ej of the solutions with different concentrations, sequentially calculating the measured values in the matrix a0 by the central control system and generating a potential correction value matrix e0, and generating a standard curve and a function corresponding to the standard curve by the central control system according to e 0;
and (3) diluting the sample to be detected with the mass M, filtering the sample to be detected into a sample solution, dissolving the sample, detecting the potential value a of the sample solution, transmitting the detection result to a central control system, and comparing the internal parameters a and a0 by the central control system to adjust the sampling quality.
Specifically, when a is within a preset range, pouring another sample into the calcium ion absorption device to extract calcium ions in the solution; detecting the potential value az of the extracted calcium ion sample solution; the central control system calculates the potential value ratio H of the sample solution after the extraction of the calcium ions and the sample solution before the extraction of the calcium ions, compares H with a potential difference ratio parameter H, judges whether interference ions exist in the sample solution or not, judges more interference ions exist in the sample solution, corrects the potential value of the sample solution before the extraction of the calcium ions, calculates a potential correction value ex of the sample solution according to a correction value, brings the ex into a function corresponding to the standard curve to obtain the concentration Gx of the calcium ions in the sample solution, and calculates the content X of the calcium in the sample according to the Gx.
Weighing 1.11g of calcium chloride reagent which is burned at 550 ℃ for 1h and cooled, placing the reagent in a beaker, adding water to dissolve the reagent, transferring the reagent into a volumetric flask with 100mL, diluting the reagent to a scale with water, shaking up the reagent to prepare a standard calcium chloride solution with 0.1mol/L, wherein the content of calcium ions in the solution is 4 mg/mL;
the central control system is provided with a standard calcium chloride solution transfer amount matrix A0 (A1, A2, A3, A4, A5 and A6), wherein A1 is a first preset transfer amount, A2 is a second preset transfer amount, A3 is a third preset transfer amount, A4 is a fourth preset transfer amount, A5 is a fifth preset transfer amount, A6 is a sixth preset transfer amount, and the values of the transfer amounts are sequentially increased;
transferring the transfer amounts arranged in the matrix A0 to different beakers in sequence and accurately, adding pure water to dissolve the calcium ions, transferring the calcium ions to 50mL volumetric flasks respectively after the calcium ions are dissolved, diluting the calcium ions to scales by using water to obtain calcium ion standard series solutions with different concentrations, generating a calcium ion standard series solution concentration matrix G0 (G1, G2, G3, G4, G5 and G6) by a central control system, wherein G1 corresponds to the solution concentration of a first preset transfer amount, G2 corresponds to the solution concentration of a second preset transfer amount, G3 corresponds to the solution concentration of a third preset transfer amount, G4 corresponds to the solution concentration of a fourth preset transfer amount, G5 corresponds to the solution concentration of a fifth preset transfer amount, and G6 corresponds to the solution concentration of a sixth preset transfer amount.
Specifically, a calcium ion selective electrode and a saturated calomel electrode are correctly connected with an acidimeter, the electrodes are inserted into a plastic beaker filled with 50mL of water, an instrument is preheated, the materials are stirred on a magnetic stirrer at a constant speed, potential measurement can be carried out after the potential is stable, a blank condition potential value E is recorded, and a detection result is transmitted to a central control system;
a blank potential value numerical value matrix E0 and a compensation parameter calculation parameter matrix BO of the blank potential value to the measured potential value are arranged in the central control system;
for the blank potential value matrices E0, E0(E1, E2, E3, E4), where E1 is a first preset number of blank potential values, E2 is a second preset number of blank potential values, E3 is a third preset number of blank potential values, E4 is a fourth preset number of blank potential values, each of said values increasing in order;
calculating a parameter matrix BO, B0(B1, B2, B3, B4) for a compensation parameter of a blank potential value to a measured potential value, wherein B1 is a compensation parameter calculation parameter of a first preset blank potential value to a measured potential value, B2 is a compensation parameter calculation parameter of a second preset blank potential value to a measured potential value, B3 is a compensation parameter calculation parameter of a third preset blank potential value to a measured potential value, and B4 is a compensation parameter calculation parameter of a fourth preset blank potential value to a measured potential value;
the central control system compares the internal parameters of E and E0:
when E is less than or equal to E1, the central control system does not compensate and calculate the measured potential value according to the blank potential value;
when E is more than E1 and less than or equal to E2, the central control system selects B1 from the B0 matrix as a compensation parameter calculation parameter of the blank potential value to the measured potential value;
when E is more than E2 and less than or equal to E3, the central control system selects B2 from the B0 matrix as a compensation parameter calculation parameter of the blank potential value to the measured potential value;
when E is more than E3 and less than or equal to E4, the central control system selects B3 from the B0 matrix as a compensation parameter calculation parameter of the blank potential value to the measured potential value;
when E is larger than E4, the central control system selects B4 from the B0 matrix as a compensation parameter calculation parameter of the blank potential value to the measured potential value;
when the measured potential value needs to be compensated, the central control system calculates a compensation parameter C, C = (E-E1). times.Bi, i =1,2,3,4 of the blank potential value to the measured potential value.
Specifically, calcium ion standard series solutions with different concentrations are detected in sequence to obtain measured values of each standard solution, each measured value is input into a central control system, and the central control system generates a standard series solution measured value matrix a0 (a1, a2, A3, a4, a5 and A6), wherein a1 is a1 transfer amount standard solution measured value, a2 is a2 transfer amount standard solution measured value, A3 is A3 transfer amount standard solution measured value, a4 is a4 transfer amount standard solution measured value, a5 is a5 transfer amount standard solution measured value, and A6 is A6 transfer amount standard solution measured value;
the central control system performs compensation on each measured value in the matrix a0 according to a compensation parameter C, and calculates potential compensation values ej, j =1,2,3,4,5,6, ej = aj-aj × C of each concentration solution;
the central control system calculates the measurement values in the matrix a0 in sequence and generates a potential correction value matrix e0(e1, e2, e3, e4, e5 and e 6);
specifically, the central control system generates a calcium ion concentration and potential correction value standard curve and generates a corresponding functional formula G = f (e) according to a potential correction value matrix e0 and a calcium ion standard series solution concentration matrix G0, and e ∈ [ e1, eg ].
Specifically, the central control system is further provided with a sample sampling quality compensation parameter matrix N0 (N1, N2), wherein N1 is a sample sampling quality compensation parameter with too low a potential value, and N2 is a sample sampling quality compensation parameter with high and low potential values.
Putting a sample to be detected with the mass M into an iodometry bottle, adding 100mL of 1mol/L hydrochloric acid into the iodometry bottle, putting a stirrer into the iodometry bottle, and stirring on a magnetic stirrer for T1; after stirring, putting a proper amount of solution into a 50mL centrifuge tube, and centrifuging for T2 time in a centrifuge at the rotating speed of 4000 r/min; after centrifugation, respectively taking 10mL of supernatant in two beakers, respectively adding a proper amount of ultrapure water into each beaker, adjusting the pH to 7.5 by using a 50% triethanolamine solution, respectively adding 4mL of 1mol/L KCl solution into each beaker after the pH value of the solution is stable, respectively transferring the solution into two 50mL volumetric flasks, and metering to the scale with water.
Specifically, a sample solution is poured into a plastic beaker, the potential value a of the sample solution is detected, and the detection result is transmitted to a central control system, and the central control system compares the internal parameters a and a 0:
when a is greater than or equal to a1 and less than a6, the central control system judges that the potential value is in a reasonable measurement range and does not adjust the sampling quality of the sample;
when a is not in the range of a1-a 6, the central control system judges that the potential value is not in the reasonable measurement range, and adjusts the sampling quality of the sample;
when a is less than a1, the central control system selects N1 from the matrix N0 as a sample sampling quality compensation parameter, and calculates a sample sampling quality correction value M ', M' = (a 1-a). times.N 1/a 1;
when a is larger than or equal to a6, the central control system selects N2 from the matrix N0 as a sample sampling quality compensation parameter, and the central control system calculates a sample sampling quality correction value M ', M' = a6 multiplied by N2 divided by (a-a 6).
Specifically, when the central control system corrects the sampling quality of the sample to M ', the sample dissolving operation is repeated, and the potential value a ' of the sample solution when the sampling quality is M ' is detected, the central control system compares the internal parameters a ' and a0, and when a1 is more than or equal to a ' < a6, the central control system judges that the potential value does not adjust the sampling quality of the sample within a reasonable measurement range; when a is not in the range of a1-a 6, repeating the sample quality correction operation until a1 is not more than or equal to a' < a 6;
when a is more than or equal to a1 and less than a6, pouring the other sample into a calcium ion absorption device to extract calcium ions in the solution.
Specifically, when calcium ions are extracted from a sample solution, the central control system starts the first circulator and the second circulator, closes the first valve and opens the second valve, and the sample solution circulates in the calcium ion absorption device under the action of each circulator, wherein the circulation time is T3, T3= (a-a 1). times.alpha + T, wherein alpha is a potential value of the sample solution and a compensation parameter of the circulation time, and T is a basic value of the circulation time.
Specifically, the central control system is also provided with a potential difference ratio parameter H;
when the circulation time of the sample solution in the calcium ion absorption device reaches T3, the central control system controls the second circulator to stop working, opens the first valve and closes the second valve, the sample solution is discharged into a plastic beaker, and the potential value az of the extracted calcium ion sample solution is detected; the central control system calculates the potential value ratio H, H = az ÷ a of the sample solution after the extraction of the calcium ions and the sample solution before the extraction of the calcium ions, and compares H with H:
when H is less than H, the central control system judges that interference ions in the sample solution are less and does not correct the potential value of the sample solution before calcium ion extraction;
when H is larger than or equal to H, the central control system judges that the number of interference ions in the sample solution is large, the potential value of the sample solution before calcium ion extraction is corrected, the corrected sample value is ax, ax = (a-az) ÷ Z, and Z is a correction parameter of the potential value of the interference ions;
the central control system calculates the potential correction value ex of the sample solution, when H is less than H, ex = a-a × C, and when H is more than or equal to H, ex = ax-ax × C.
Specifically, the central control system brings the potential correction value ex of the sample solution into a curve function formula G = f (e), e belongs to [ e1, eg ], and calculates the concentration Gx of calcium ions in the sample solution;
the central control system calculates the content X of calcium in the sample through the concentration Gx of calcium ions in the sample:
X= Gx×K÷1000÷M’×100％
and K is a compensation parameter of the dilution multiple to the calcium ion concentration of the sample.
So far, the technical solutions of the present invention have been described in connection with the preferred embodiments shown in the drawings, but it is easily understood by those skilled in the art that the scope of the present invention is obviously not limited to these specific embodiments. Equivalent changes or substitutions of related technical features can be made by those skilled in the art without departing from the principle of the invention, and the technical scheme after the changes or substitutions can fall into the protection scope of the invention.
Claims (8)
1. A method for measuring the content of calcium in feed by using an ion selective electrode is characterized by comprising the following steps:
s1, preparing 0.1mol/L standard calcium chloride solution, accurately transferring a specified amount of standard calcium chloride solution, and diluting to obtain various calcium chloride solutions with specific concentrations;
s2, potential values of calcium chloride solutions with different specific concentrations are determined through a primary battery test, and the potential values and the concentration values are input into a central control system of the values to generate a standard curve and a function corresponding to the standard curve;
s3, melting and diluting the sample to be detected, and detecting the potential value of the sample solution;
s4, removing calcium ions in the sample to be detected, detecting the potential value of the sample solution after the extraction of the calcium ions, and judging whether interference ions exist or not;
s5, revising the potential value, calculating the content of calcium ions in the solution according to the revised potential value and the standard curve, and calculating the content of calcium in the sample according to the content of calcium ions;
a central control system is arranged in the process of adopting the method for measuring the calcium content in the feed by utilizing the ion selective electrode; the central control system is provided with a standard calcium chloride solution transfer amount matrix A0, the transfer amounts arranged in the matrix A0 are sequentially and accurately transferred to different beakers, calcium ion standard series solutions with different concentrations are obtained by diluting with water, and a calcium ion standard series solution concentration matrix G0 is generated;
a blank potential value numerical value matrix E0 and a compensation parameter calculation parameter matrix BO of the blank potential value to the measured potential value are arranged in the central control system; measuring a blank potential value E and transmitting a detection result to the central control system, wherein the central control system calculates a compensation parameter C of the blank potential value to the measured potential value according to the E; detecting calcium ion standard series solutions with different concentrations in sequence to obtain measured values of each standard solution, generating a standard series solution measured value matrix a0 by a central control system, compensating the measured values in the matrix a0 according to a compensation parameter C by the central control system, calculating potential correction values ej of the solutions with different concentrations, sequentially calculating the measured values in the matrix a0 by the central control system and generating a potential correction value matrix e0, and generating a standard curve and a function corresponding to the standard curve by the central control system according to e 0;
diluting a sample to be detected with the mass M, filtering the sample to be detected into a sample solution, dissolving the sample, detecting the potential value a of the sample solution, transmitting the detection result to a central control system, and comparing the internal parameters a and a0 by the central control system to adjust the sampling quality;
when a is in a preset range, pouring the other sample into a calcium ion absorption device to extract calcium ions in the solution; detecting the potential value az of the extracted calcium ion sample solution; the central control system calculates the potential value ratio H of the sample solution after the extraction of the calcium ions and the sample solution before the extraction of the calcium ions, compares H with a potential difference ratio parameter H, judges whether interference ions exist in the sample solution or not, judges more interference ions exist in the sample solution, corrects the potential value of the sample solution before the extraction of the calcium ions, calculates a potential correction value ex of the sample solution according to a correction value, brings the ex into a function corresponding to the standard curve to obtain the concentration Gx of the calcium ions in the sample solution, and calculates the content X of the calcium in the sample according to the Gx.
2. The method for determining calcium content in feedstuff using ion selective electrode according to claim 1, wherein for the standard calcium chloride solution removal matrix a0, a0 (a1, a2, A3, a4, a5, A6), wherein a1 is a first predetermined removal amount, a2 is a second predetermined removal amount, A3 is a third predetermined removal amount, a4 is a fourth predetermined removal amount, a5 is a fifth predetermined removal amount, A6 is a sixth predetermined removal amount, each of said removal amount values is increased in order;
for the standard series solution measurement matrix a0, a0 (a1, a2, A3, a4, A5, A6), where a1 is a1 pipetting standard solution measurement, a2 is a2 pipetting standard solution measurement, A3 is A3 pipetting standard solution measurement, a4 is a4 pipetting standard solution measurement, A5 is A5 pipetting standard solution measurement, and A6 is A6 pipetting standard solution measurement;
the calcium ion suction device with the central control system links to each other, and the calcium ion suction device includes: the device comprises a calcium ion absorption net, a liquid injection port plug, a first circulating machine, a second circulating machine, a circulating channel, a first valve, a second valve and a liquid storage bin, wherein the liquid storage bin is used for storing a sample solution to be separated; the calcium ion absorption net is positioned in the liquid storage bin and divides the liquid storage bin into two parts, and a protein carrier capable of absorbing calcium ions is arranged on the calcium ion absorption net; the liquid injection port is positioned at the top of the calcium ion absorption device and is used for injecting a sample solution to be separated into the liquid storage bin; the liquid injection port plug is positioned at the upper part of the liquid injection port, so that liquid splashing is prevented when the sample solution circulates; the first circulating machine is positioned at the initial end of the circulating channel, the second circulating machine is positioned at the tail end of the circulating channel, and each circulating machine is used for circulating the sample solution to be separated in the liquid storage bin; the first valve is connected with the external interface and used for sucking and discharging the sample solution completely by calcium ions; the second valve is arranged on the circulating channel;
when calcium ions are extracted from the sample solution, the central control system starts the first circulator and the second circulator, closes the first valve and opens the second valve, the sample solution circulates in the calcium ion absorption device under the action of each circulator, the circulation time is T3, T3= (a-a 1). times.alpha + T, wherein alpha is a compensation parameter of the potential value of the sample solution to the circulation time, and T is a basic value of the circulation time;
the central control system is also provided with a potential difference ratio parameter H;
when the circulation time of the sample solution in the calcium ion absorption device reaches T3, the central control system controls the second circulator to stop working, opens the first valve and closes the second valve, the sample solution is discharged into a plastic beaker, and the potential value az of the extracted calcium ion sample solution is detected; the central control system calculates the potential value ratio H, H = az ÷ a of the sample solution after the extraction of the calcium ions and the sample solution before the extraction of the calcium ions, and compares H with H:
when H is less than H, the central control system judges that interference ions in the sample solution are less and does not correct the potential value of the sample solution before calcium ion extraction;
and when H is larger than or equal to H, the central control system judges that the interference ions in the sample solution are more, the potential value of the sample solution before the calcium ion extraction is corrected, the corrected sample value is ax, ax = (a-az) ÷ Z, and Z is a correction parameter of the potential value of the interference ions.
3. The method for measuring the content of calcium in the feed by using the ion selective electrode as claimed in claim 2, wherein the calcium ion selective electrode and the saturated calomel electrode are correctly connected with an acidimeter, the electrodes are inserted into a plastic beaker filled with 50mL of water, an instrument is preheated, the materials are stirred on a magnetic stirrer at a constant speed, after the potential is stabilized, the potential measurement can be carried out, the potential value E under the blank condition is recorded, and the detection result is transmitted to a central control system;
for the blank potential value matrices E0, E0(E1, E2, E3, E4), where E1 is a first preset number of blank potential values, E2 is a second preset number of blank potential values, E3 is a third preset number of blank potential values, E4 is a fourth preset number of blank potential values, each of said values increasing in order;
calculating a parameter matrix BO, B0(B1, B2, B3, B4) for a compensation parameter of a blank potential value to a measured potential value, wherein B1 is a compensation parameter calculation parameter of a first preset blank potential value to a measured potential value, B2 is a compensation parameter calculation parameter of a second preset blank potential value to a measured potential value, B3 is a compensation parameter calculation parameter of a third preset blank potential value to a measured potential value, and B4 is a compensation parameter calculation parameter of a fourth preset blank potential value to a measured potential value;
the central control system compares the internal parameters of E and E0:
when E is less than or equal to E1, the central control system does not compensate and calculate the measured potential value according to the blank potential value;
when E is more than E1 and less than or equal to E2, the central control system selects B1 from the B0 matrix as a compensation parameter calculation parameter of the blank potential value to the measured potential value;
when E is more than E2 and less than or equal to E3, the central control system selects B2 from the B0 matrix as a compensation parameter calculation parameter of the blank potential value to the measured potential value;
when E is more than E3 and less than or equal to E4, the central control system selects B3 from the B0 matrix as a compensation parameter calculation parameter of the blank potential value to the measured potential value;
when E is larger than E4, the central control system selects B4 from the B0 matrix as a compensation parameter calculation parameter of the blank potential value to the measured potential value;
when the measured potential value needs to be compensated, the central control system calculates a compensation parameter C, C = (E-E1). times.Bi, i =1,2,3,4 of the blank potential value to the measured potential value.
4. The method for determining calcium content in feed by using ion selective electrode as claimed in claim 3, wherein the set transfer amount in matrix A0 is sequentially transferred to different beakers, after being dissolved by adding pure water, the beakers are respectively transferred to 50mL volumetric flasks and diluted to the scale with water to obtain calcium ion standard series solutions with different concentrations, the central control system generates calcium ion standard series solution concentration matrix G0 (G1, G2, G3, G4, G5, G6), wherein G1 is the solution concentration corresponding to the first preset transfer amount, G2 is the solution concentration corresponding to the second preset transfer amount, G3 is the solution concentration corresponding to the third preset transfer amount, G4 is the solution concentration corresponding to the fourth preset transfer amount, G5 is the solution concentration corresponding to the fifth preset transfer amount, and G6 is the solution concentration corresponding to the sixth preset transfer amount;
detecting calcium ion standard series solutions with different concentrations in sequence to obtain measured values of each standard solution, inputting each measured value into a central control system, and generating a standard series solution measured value matrix a0 (a1, a2, A3, a4, a5 and A6) by the central control system, wherein a1 is a measured value of a1 transfer quantity standard solution, a2 is a measured value of a2 transfer quantity standard solution, A3 is a measured value of A3 transfer quantity standard solution, a4 is a measured value of a4 transfer quantity standard solution, a5 is a measured value of a5 transfer quantity standard solution, and A6 is a measured value of A6 transfer quantity standard solution;
the central control system performs compensation on each measured value in the matrix a0 according to a compensation parameter C, and calculates potential compensation values ej, j =1,2,3,4,5,6, ej = aj-aj × C of each concentration solution;
the central control system calculates the measurement values in the matrix a0 in sequence and generates a potential correction value matrix e0(e1, e2, e3, e4, e5 and e 6).
5. The method for determining the content of calcium in feed by using the ion selective electrode as claimed in claim 4, characterized in that the central control system generates a standard curve of calcium ion concentration and potential correction value according to the potential correction value matrix e0 and the calcium ion standard series solution concentration matrix G0 and generates a corresponding functional formula G = f (e), e ∈ [ e1, eg).
6. The method for measuring the content of calcium in feed by using the ion selective electrode as claimed in claim 5, wherein the central control system calculates the potential correction value ex of the sample solution, ex = a-axxc when H < H, and ex = ax-axxc when H ≧ H;
the central control system brings the potential correction value ex of the sample solution into a curve function formula G = f (e), e belongs to [ e1, eg ], and the concentration Gx of calcium ions in the sample solution is calculated;
the central control system calculates the content X of calcium in the sample through the concentration Gx of calcium ions in the sample:
X=Gx×K÷1000÷M’×100％
wherein K is a parameter for compensating the calcium ion concentration of the sample by the dilution factor, and M' is the sampling quality of the sample to be detected.
7. The method for determining the calcium content in the feed by using the ion selective electrode according to claim 1, wherein a sample to be detected with the mass M is placed into an iodometric flask, 100mL of 1mol/L hydrochloric acid is added into the iodometric flask, a stirrer is placed into the iodometric flask and stirred on a magnetic stirrer, and the stirring time is T1; after stirring, putting a proper amount of solution into a 50mL centrifuge tube, and centrifuging for T2 time in a centrifuge at the rotating speed of 4000 r/min; after centrifugation, respectively taking 10mL of supernatant in two beakers, respectively adding a proper amount of ultrapure water into each beaker, adjusting the pH to 7.5 by using a 50% triethanolamine solution, respectively adding 4mL of 1mol/L KCl solution into each beaker after the pH value of the solution is stable, respectively transferring the solution into two 50mL volumetric flasks, and metering to the scale with water.
8. The method for determining calcium content in feed by using ion selective electrode as claimed in claim 7, characterized in that, a sample solution is poured into a plastic beaker, the potential value a of the sample solution is detected and the detection result is transmitted to the central control system, the central control system compares a with the internal parameters of a 0:
when a is greater than or equal to a1 and less than a6, the central control system judges that the potential value is in a reasonable measurement range and does not adjust the sampling quality of the sample;
when a is not in the range of a1-a 6, the central control system judges that the potential value is not in the reasonable measurement range, and adjusts the sampling quality of the sample;
when a is less than a1, the central control system selects N1 from the matrix N0 as a sample sampling quality compensation parameter, and calculates a sample sampling quality correction value M ', M' = (a 1-a). times.N 1/a 1;
when a is larger than or equal to a6, the central control system selects N2 from the matrix N0 as a sample sampling quality compensation parameter, and the central control system calculates a sample sampling quality correction value M ', M' = a6 multiplied by N2 divided by (a-a6);
when the sampling quality of the sample is corrected to M ' by the central control system, repeating the sample dissolving operation and detecting the potential value a ' of the sample solution when the sampling quality is M ', wherein the central control system compares the a ' with the internal parameters of a0, and when a1 is not more than a ' < a6, the central control system judges that the potential value does not adjust the sampling quality of the sample within a reasonable measurement range; when a is not in the range of a1-a 6, repeating the sample quality correction operation until a1 is not more than or equal to a' < a 6;
when a is more than or equal to a1 and less than a6, pouring the other sample into a calcium ion absorption device to extract calcium ions in the solution.
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