CN114923970A - PVC calcium ion selective electrode and preparation method thereof - Google Patents
PVC calcium ion selective electrode and preparation method thereof Download PDFInfo
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- CN114923970A CN114923970A CN202210467861.5A CN202210467861A CN114923970A CN 114923970 A CN114923970 A CN 114923970A CN 202210467861 A CN202210467861 A CN 202210467861A CN 114923970 A CN114923970 A CN 114923970A
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- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910001424 calcium ion Inorganic materials 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 22
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 22
- 229910021538 borax Inorganic materials 0.000 claims abstract description 11
- 150000003983 crown ethers Chemical class 0.000 claims abstract description 11
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 11
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000012528 membrane Substances 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 15
- 229920003023 plastic Polymers 0.000 claims description 15
- 239000004033 plastic Substances 0.000 claims description 15
- 239000004014 plasticizer Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 11
- 150000001768 cations Chemical class 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 9
- 238000005520 cutting process Methods 0.000 claims description 8
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical group O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 claims description 8
- 239000011159 matrix material Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- 239000002555 ionophore Substances 0.000 claims description 5
- 230000000236 ionophoric effect Effects 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical group CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 14
- 239000011575 calcium Substances 0.000 abstract description 7
- 238000001514 detection method Methods 0.000 abstract description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 2
- 230000004044 response Effects 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 239000000843 powder Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 9
- 229910021607 Silver chloride Inorganic materials 0.000 description 8
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 8
- 238000005303 weighing Methods 0.000 description 6
- 238000012544 monitoring process Methods 0.000 description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 239000001110 calcium chloride Substances 0.000 description 4
- 229910001628 calcium chloride Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000003631 expected effect Effects 0.000 description 2
- 239000008233 hard water Substances 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 208000037147 Hypercalcaemia Diseases 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- -1 calcium carbonate Chemical class 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002795 fluorescence method Methods 0.000 description 1
- 230000007661 gastrointestinal function Effects 0.000 description 1
- 230000000148 hypercalcaemia Effects 0.000 description 1
- 208000030915 hypercalcemia disease Diseases 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
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Classifications
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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
- G01N27/3335—Ion-selective electrodes or membranes the membrane containing at least one organic component
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- 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)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
The invention discloses a PVC calcium ion selective electrode and a preparation method thereof. The sensing film is prepared by taking polyvinyl chloride as a film skeleton and adding dibutyl phthalate, sodium tetraborate and crown ether dissolved in tetrahydrofuran. The concentration of calcium ions in water is converted into potential difference by connecting a reference electrode and a potential detection module, and then is converted into the concentration of the calcium ions by an nernst equation. In the presence of Al 3+ 、Fe 3+ 、Cu 2+ For Ca in the case of 2+ Has better selectivity. The method can be used for directly detecting on site, and has the advantages of simple operation, low cost and the like.
Description
Technical Field
The invention designs a preparation method of a calcium ion selective electrode, which belongs to the field of electrochemistry and can be used for measuring the content of calcium ions in water hardness.
Background
The hardness of water is the content of calcium salt and magnesium salt dissolved in water, and if the content is small, the hardness of water is small, otherwise, the hardness is large, and if people who drink hard water infrequently drink hard water accidentally, the gastrointestinal function of the people is disturbed. The daily intake of calcium in human body should not be higher than 2500mg, otherwise, it will result in hypercalcemia, kidney damage, and also affect the absorption of other minerals. If the concentration of calcium ions in the water body is too high, precipitates can be formed with some anions, such as calcium carbonate, if the calcium ions are attached to pipelines of a circulating water system, firstly, the circulating water circulation area is reduced, a heat exchanger and the like are blocked, secondly, the circulating water system is directly contacted with the atmosphere, and the water temperature is controlled below 30 ℃, so that the calcium ion water circulating system is very suitable for breeding bacteria and algae, and the calcium ion water circulating system can be attached to the calcium precipitates to form dirt, corrode metal pipelines and the like. The conventional calcium ion detection methods mainly comprise an atomic absorption method, a colorimetric titration method, a fluorescence method and the like, but the methods and the instruments have the defects of high cost, low analysis speed, large device volume and the like, so the conventional calcium ion detection methods are only suitable for laboratory analysis and cannot carry out field real-time monitoring.
The first development of ion selective electrodes is calcium ion selective electrodes, which are a class of electrochemical sensors that utilize membrane potential to determine the concentration or activity of ions in a solution. The most important part of the calcium ion selective electrode is the calcium ion sensitive membrane, and the selectivity and stability of the membrane are the key points of research and development. Experiments prove that crown ether and Ca dissolved in water 2+ The crown ether has the characteristics of excellent interaction, reasonable dissociation activity of the formed complex and urgent requirement of the crown ether as an ion selective electrode. Membrane ion separation currently using PVC as raw materialThe selective electrode is the most widely applied potential sensor at present, has advantages in price, is not easily influenced by samples, is easy to realize field monitoring, and has an important role in calcium ion detection.
Disclosure of Invention
The invention aims to develop a calcium ion selective electrode convenient for on-site monitoring. The main technology of the electrode lies in the preparation of a calcium ion sensitive membrane. The prepared ion selective electrode and the reference electrode are connected with a sensor, and can be used for on-site continuous monitoring.
A PVC calcium ion selective electrode is composed of a metal wire, an internal filling liquid and a calcium ion sensitive film; the calcium ion sensitive membrane takes crown ether as an ionophore, takes PVC as a polymer matrix, takes esters as a plasticizer and takes sodium tetraborate as a cation exchanger; wherein the mass ratio of the polymer matrix to the ionophore to the plasticizer to the cation exchanger is 180-220: 40-60: 200-400: 1 to 15.
In some preferred embodiments: the mass ratio of the polymer matrix to the ionophore to the plasticizer to the cation exchanger is 180-220: 40-60: 200-400: 5 to 7.
The technical scheme of the invention is as follows: the material of the metal wire is silver.
In the technical scheme of the invention: the mass ratio of the polymer matrix to the plasticizer is 1: 1 to 2.
The technical scheme of the invention is as follows: the crown ether is dibenzo-18-crown-6.
The technical scheme of the invention is as follows: the plasticizer is tributyl phosphate or dibutyl phthalate.
The preparation method of the PVC calcium ion selective electrode comprises the following steps:
(1) preparation of the Plastic housing
Manufacturing a plastic shell into a cylinder, fixing the silver wire at one end and then sealing, and manufacturing the other end into a honeycomb shape;
(2) preparation of the internal filling liquid
Preparing a calcium chloride solution;
(3) preparation of sensitive film
Dissolving polyvinyl chloride in an organic solvent, adding a plasticizer after dissolving, then adding crown ether and a cation exchanger, uniformly stirring, pouring into a glass plate, and standing for 40-60 hours under natural conditions;
(4) preparation of the electrodes
And filling the inner filling liquid into the shell, cutting the prepared sensitive film into a wafer with the diameter of 0.5-3 cm, attaching the sensitive film to the other end of the shell by using 5% PVC-THF, and standing for 24 hours under natural conditions to obtain the target product.
The technical scheme of the invention is as follows: the inner filling liquid is 0.1mol/L calcium chloride.
In the technical scheme of the invention: the organic solvent tetrahydrofuran is a colorless volatile liquid, can be used as a precursor of a high molecular polymer, is generally used in an amount of 5-10 ml when a membrane ion electrode is manufactured, and can be adjusted according to the amount of PVC.
The method comprises the following steps: the plastic shell in the step (1) is a cylinder with the diameter of 1cm and the height of 4 cm.
The method comprises the following steps: the diameter of the sensitive membrane in the step (4) is 1 cm.
The experimental conditions and results of the invention are as follows: the prepared ion selective electrode and the purchased reference electrode are connected with a sensor, the probe is placed in the same known concentration gradient solution, and the result accords with the Nernst equation through the PC end test, and the response slope reaches 30.7 mV/dec.
Has the advantages that:
the calcium ion selective electrode prepared by the invention is convenient for on-site monitoring. In the preparation raw materials of the calcium ion sensitive membrane, the electroactive compound is low in price and easy to purchase in the market, and crown ether is used as the electroactive substance, so that the interference of other metal ions is reduced. Dibutyl phthalate is selected as a plasticizer, so that the response performance of the electrode can be improved, and a cation exchanger sodium tetraborate is added to promote the ion exchange process, so that the response performance to target ions is optimized. The ion selective electrode has the characteristics of strong selectivity, low detection lower limit, short response time and good reproducibility, is convenient and quick to operate, is an ideal detection tool, and has wide application prospects in the aspects of water hardness detection and the like.
Drawings
FIG. 1 is a basic structure diagram of a PVC calcium ion selective electrode;
fig. 2, 3 and 4 are response slopes of the membrane electrodes prepared in examples 1, 2 and 3, respectively.
Detailed Description
The invention is further illustrated by the following examples, without limiting the scope of the invention:
the electrode plastic shell is manufactured in advance and is internally filled with 0.1mol/LCaCl liquid 2 And (3) solution.
Preparing a plastic shell: manufacturing the plastic shell into a cylinder, fixing the silver wire at one end and then sealing, and manufacturing the other end into a honeycomb shape; the plastic shell is a cylinder with the diameter of 1cm and the height of 4 cm.
Example 1
(1) Preparation of sensitive film
Weighing 0.20g of PVC powder, dissolving in 5ml of THF, stirring until the powder is completely dissolved, adding 0.20g of dibutyl phthalate, 0.05g of dibenzo-18-crown-6 and 5mg of sodium tetraborate, stirring uniformly, pouring onto a flat plate, and standing for 48h under natural conditions to obtain the elastic film.
(2) Preparation of the electrodes
Cutting the obtained elastic membrane into circular pieces with diameter of 1cm, sticking the circular pieces to the bottom of a plastic shell containing internal filling liquid by using 5% PVC-THF solution, standing for 24h under natural condition, and adding 0.1mol/LCaCl 2 Activation in solution was carried out for two hours.
(3) Electrode performance testing
The electrode and an Ag/AgCl reference electrode are placed at 10 -4 、10 -3 、10 -2 、10 -1 In mol/L calcium chloride solution, the sensor is connected, and the data read from the PC end conforms to the Nernst equation, and the response slope is 30.7 mV/dec.
Example 2
(1) Preparation of sensitive film
Weighing 0.20g of PVC powder, dissolving in 5ml of LTHF, stirring until the powder is completely dissolved, adding 0.30g of dibutyl phthalate, 0.05g of dibenzo-18-crown ether-6 and 6mg of sodium tetraborate, uniformly stirring, pouring onto a flat plate, and standing for 48h under natural conditions to obtain the elastic membrane.
(2) Preparation of the electrodes
Cutting the obtained elastic membrane into circular pieces with diameter of 1cm, sticking the circular pieces to the bottom of a plastic shell containing internal filling liquid by using 5% PVC-THF solution, standing for 24h under natural condition, and adding 0.1mol/LCaCl 2 Activation in solution was carried out for two hours.
(3) Electrode performance testing
The electrode and an Ag/AgCl reference electrode are placed at 10 -4 、10 -3 、10 -2 、10 -1 In mol/L calcium chloride solution, the sensor is connected, and the data read from the PC end are found to conform to the Nernst equation, and the response slope is 25.8 mV/dec.
Example 3
(1) Preparation of sensitive film
Weighing 0.20g of PVC powder, dissolving in 5ml of LTHF, stirring until the powder is completely dissolved, adding 0.40g of dibutyl phthalate, 0.05g of dibenzo-18-crown ether-6 and 7mg of sodium tetraborate, uniformly stirring, pouring onto a flat plate, and standing for 48h under natural conditions to obtain the elastic membrane.
(2) Preparation of the electrodes
Cutting the obtained elastic membrane into circular pieces with diameter of 1cm, sticking the circular pieces to the bottom of a plastic shell containing internal filling liquid by using 5% PVC-THF solution, standing for 24h under natural condition, and adding 0.1mol/LCaCl 2 The solution was activated for two hours.
(3) Electrode performance testing
The electrode and an Ag/AgCl reference electrode are placed at 10 -4 、10 -3 、10 -2 、10 -1 In mol/L calcium chloride solution, a sensor is connected, and the data read from the PC end conforms to the Nernst equation, and the response slope is 23.8 mV/dec.
Example 4
(1) Preparation of sensitive film
Weighing 0.20g of PVC powder, dissolving in 5ml of THF, stirring until the powder is completely dissolved, adding 0.20g of dibutyl phthalate, 0.05g of dibenzo-18-crown-6 and 5mg of sodium tetraborate, stirring uniformly, pouring onto a flat plate, and standing for 48h under natural conditions to obtain the elastic film.
(2) Preparation of the electrodes
Cutting the elastic membrane into circular sheet with diameter of 1cm, sticking it on the bottom of plastic shell containing inner filling liquid with 5% PVC-THF solution, standing for 24 hr under natural condition, and adding 0.1mol/LCaCl 2 The solution was activated for two hours.
(3) Electrode performance testing
The electrode and an Ag/AgCl reference electrode are placed at 10 -4 、10 -3 、10 -2 、10 -1 mol/L calcium chloride, copper chloride and aluminum chloride, wherein Ca 2+ ：Cu 2+ ：Al 3+ In a molar ratio of 1: 1: 1, the sensor is connected, and the data read from the PC terminal conforms to the Nernst equation, and the response slope of the sensor is 30.5 mV/dec.
Example 5
(1) Preparation of sensitive film
Weighing 0.20g of PVC powder, dissolving in 5ml of LTHF, stirring until the powder is completely dissolved, adding 0.30g of dibutyl phthalate, 0.05g of dibenzo-18-crown ether-6 and 6mg of sodium tetraborate, uniformly stirring, pouring onto a flat plate, and standing for 48h under natural conditions to obtain the elastic membrane.
(2) Preparation of the electrodes
Cutting the obtained elastic membrane into circular pieces with diameter of 1cm, sticking the circular pieces to the bottom of a plastic shell containing internal filling liquid by using 5% PVC-THF solution, standing for 24h under natural condition, and adding 0.1mol/LCaCl 2 The solution was activated for two hours.
(3) Electrode performance testing
The electrode and an Ag/AgCl reference electrode are placed at 10 -4 、10 -3 、10 -2 、10 -1 In the mixed solution of calcium chloride, ferric chloride and copper chloride in mol/L, wherein Ca is 2+ ：Fe 3+ ：Cu 2+ In a molar ratio of 1: 1: 1, connecting a sensor, and finding out the coincidence with Nernst square from data read out from a PC terminalThe slope of the response is 25.5 mV/dec.
Example 6
(1) Preparation of sensitive film
Weighing 0.20g of PVC powder, dissolving in 5ml of LTHF, stirring until the powder is completely dissolved, adding 0.40g of dibutyl phthalate, 0.05g of dibenzo-18-crown ether-6 and 7mg of sodium tetraborate, uniformly stirring, pouring onto a flat plate, and standing for 48h under natural conditions to obtain the elastic membrane.
(2) Preparation of the electrodes
Cutting the obtained elastic membrane into circular pieces with diameter of 1cm, sticking the circular pieces to the bottom of a plastic shell containing internal filling liquid by using 5% PVC-THF solution, standing for 24h under natural condition, and adding 0.1mol/LCaCl 2 Activation in solution was carried out for two hours.
(3) Electrode performance testing
The electrode and an Ag/AgCl reference electrode are placed at 10 -4 、10 -3 、10 -2 、10 -1 In mol/L mixed solution of calcium chloride, ferric chloride, copper chloride and aluminum chloride, wherein Ca is contained 2+ ：Fe 3+ ：Cu 2+ ：Al 3+ In a molar ratio of 1: 1: 1: 1, connecting the sensor, finding that the data read out from the PC terminal conforms to the Nernst equation, and the response slope of the sensor is 23.7 mV/dec.
Comparative example 1
(1) Preparation of sensitive film
The conditions were the same as in example 1 except that sodium tetraborate was not added for the preparation of the sensitive film;
(2) electrode performance testing
The electrode and an Ag/AgCl reference electrode are placed at 10 -4 、10 -3 、10 -2 、10 -1 In mol/L calcium chloride solution, a sensor is connected, and the data read from the PC end conforms to the Nernst equation, and the response slope is 27.4 mV/dec.
(3) Contrast effect
Compared with the example 1, the calcium ion sensitive membrane is prepared without adding a cation exchanger, the electrode response efficiency is low, and the Nernst equation response slope does not reach the expected effect.
Comparative example 2
(1) Preparation of sensitive film
The same conditions as in example 1 were used except that the plasticizer was changed from dibutyl phthalate to tributyl phosphate in the preparation of the sensitive film;
(2) electrode performance testing
The electrode and an Ag/AgCl reference electrode are placed at 10 -4 、10 -3 、10 -2 、10 -1 In mol/L calcium chloride solution, the sensor is connected, and the data read from the PC end conforms to the Nernst equation, and the response slope is 19.4 mV/dec.
(3) Contrast effect
Compared with the example 1, when tributyl phosphate is used as a plasticizer in the preparation of the calcium ion sensitive film, the corresponding efficiency of the electrode is reduced, and the response slope of the nernst equation does not reach the expected effect.
Claims (7)
1. A PVC calcium ion selective electrode comprising: the calcium ion selective electrode consists of a metal wire, an internal filling liquid and a calcium ion sensitive film; the calcium ion sensitive membrane takes crown ether as an ion carrier, takes polyvinyl chloride as a polymer matrix, takes esters as a plasticizer and takes sodium tetraborate as a cation exchanger; wherein the mass ratio of the polymer matrix to the ionophore to the plasticizer to the cation exchanger is 180-220: 40-60: 200-400: 1 to 15.
2. The PVC calcium ion selective electrode of claim 1, wherein: the mass ratio of the polymer matrix to the ionophore to the plasticizer to the cation exchanger is 180-220: 40-60: 200-400: 5 to 7.
3. The PVC calcium ion selective electrode of claim 1, wherein: the material of the metal wire is silver.
4. The calcium ion-sensitive membrane of claim 1, wherein: the mass ratio of the polymer matrix to the plasticizer is 1: 1 to 2.
5. The calcium ion-sensitive membrane of claim 1, wherein: the crown ether is dibenzo-18-crown-6.
6. The calcium ion-sensitive membrane according to claim 1, wherein: the plasticizer is tributyl phosphate or dibutyl phthalate.
7. The preparation method of the PVC calcium ion selective electrode of claim 1, which is characterized in that: the electrode is prepared by the following method:
(1) preparation of plastic housing
Manufacturing a plastic shell into a cylinder, fixing the silver wire at one end and then sealing, and manufacturing the other end into a honeycomb shape;
(2) preparation of the internal filling liquid
Preparing a calcium chloride solution;
(3) preparation of sensitive film
Dissolving polyvinyl chloride in an organic solvent, adding a plasticizer after dissolving, then adding crown ether and a cation exchanger, uniformly stirring, pouring into a glass plate, and standing for 40-60 hours under natural conditions;
(4) preparation of the electrodes
And filling the inner filling liquid into the shell, cutting the prepared sensitive film into a wafer with the diameter of 0.5-3 cm, attaching the sensitive film to the other end of the shell by using 5% PVC-THF, and standing for 20-30 hours under natural conditions to obtain the target product.
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