CN102680551B - Organic multi-component carrier lead ion selective electrode and preparation method thereof - Google Patents
Organic multi-component carrier lead ion selective electrode and preparation method thereof Download PDFInfo
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- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 claims abstract description 60
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 58
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 claims abstract description 37
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 20
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 16
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims abstract description 15
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims description 45
- 239000012528 membrane Substances 0.000 claims description 22
- 239000004800 polyvinyl chloride Substances 0.000 claims description 17
- 239000011521 glass Substances 0.000 claims description 14
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 6
- 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 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 23
- 150000002500 ions Chemical class 0.000 abstract description 15
- 230000004044 response Effects 0.000 abstract description 14
- 229910021607 Silver chloride Inorganic materials 0.000 abstract description 13
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 abstract description 13
- 150000002678 macrocyclic compounds Chemical class 0.000 abstract description 9
- -1 sodium tetraphenylborate Chemical compound 0.000 abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 6
- 238000002464 physical blending Methods 0.000 abstract description 6
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 5
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical compound COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 abstract description 3
- 238000007385 chemical modification Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 27
- 238000012360 testing method Methods 0.000 description 19
- 238000011049 filling Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000007767 bonding agent Substances 0.000 description 6
- 230000002452 interceptive effect Effects 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 150000003983 crown ethers Chemical class 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- UOFGSWVZMUXXIY-UHFFFAOYSA-N 1,5-Diphenyl-3-thiocarbazone Chemical compound C=1C=CC=CC=1N=NC(=S)NNC1=CC=CC=C1 UOFGSWVZMUXXIY-UHFFFAOYSA-N 0.000 description 1
- PRDAVOJWDHXPPG-UHFFFAOYSA-N 1-[10,15,20-tris(2-hydroxynaphthalen-1-yl)-21,23-dihydroporphyrin-5-yl]naphthalen-2-ol Chemical class OC1=C(C2=CC=CC=C2C=C1)C1=C2C=CC(C(=C3C=CC(=C(C=4C=CC(=C(C5=CC=C1N5)C1=C(C=CC5=CC=CC=C15)O)N=4)C1=C(C=CC4=CC=CC=C14)O)N3)C1=C(C=CC3=CC=CC=C13)O)=N2 PRDAVOJWDHXPPG-UHFFFAOYSA-N 0.000 description 1
- UOEYZAXKBKAKRO-UHFFFAOYSA-N 5,11,17,23,29,35-hexa-tert-butylcalix[6]arene-37,38,39,40,41,42-hexol Chemical compound C1C(C=2O)=CC(C(C)(C)C)=CC=2CC(C=2O)=CC(C(C)(C)C)=CC=2CC(C=2O)=CC(C(C)(C)C)=CC=2CC(C=2O)=CC(C(C)(C)C)=CC=2CC(C=2O)=CC(C(C)(C)C)=CC=2CC2=CC(C(C)(C)C)=CC1=C2O UOEYZAXKBKAKRO-UHFFFAOYSA-N 0.000 description 1
- 241000258957 Asteroidea Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
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- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Abstract
The invention discloses an organic multi-component carrier lead ion selective electrode and a preparation method thereof. The organic multi-component carrier lead ion selective electrode comprises a selective film, a polrvinyl chloride pipe, an Ag/AgCl internal reference electrode, internal filled liquid and an electrode lead. The preparation method is characterized by comprising the following steps of: sufficiently mixing macrocyclic compounds such as calixarene, tetraphenylporphyrin and 18-crown ether-6 and organic matters containing soft active atoms (O, S, P), such as triphenylphosphine and dimethyl sulfide, to prepare a physical blending carrier; and dissolving the blending carrier, polrvinyl chloride powder, dibutyl phthalate and sodium tetraphenylborate into tetrahydrofuran, and carrying out ultrasonic dispersion to obtain a lead ion selective film. The purpose of carrier modification is achieved through physical mixing, so that the property of the lead ion selective electrode is extremely high, and the carrier is avoided being subjected to chemical modification with a complicated chemical synthesis process and a large quantity of organic reagents. The organic multi-component carrier lead ion selective electrode has the advantages of simple manufacturing, Nernst response, good selectivity and high stability and can be used for quickly and accurately detecting lead ions in a solution.
Description
Technical field
The invention belongs to and analyze mensuration field, particularly a kind of preparation method of the selection electrode that detects lead ion.
Background technology
Lead exceeds standard and can produce injury to environment, animal, human body etc., therefore quantitatively detects plumbum ion concentration significant.Common lead ion detection method has, atomic absorption method, spectrophotometric method, inductive coupling method, voltammetry etc.But these method complex operations, instrument costliness, cost are large, and can not realize lead ion fast, detect online.Another kind is Lead Ion-selective Electrode method, the impact that it is cheap, easy to carry, simple to operate, not to be subject to color sample and turbidity.So development Lead Ion-selective Electrode is significant.
Both at home and abroad studied go out Lead Ion-selective Electrode be the electrode concentrating on based on Polyvinylchloride (PVC) film mostly, and the core of Polyvinylchloride (PVC) membrane electrode is to select suitable carrier, according to different carriers, the selectivity of lead ion is realized to detection.Based on domestic and international Research Literature, the lead ion carrier of research mainly concentrates on macrocyclic compound [Ganjali M R at present, Norouzi P, Faridbod F, et al. One decade of research on ion-selective electrodes in iran (1996-2006). J Iran Chem Soc, 2007,4 (1): 1-29], be specifically related to crown ether derivative [Su C C, Chang M C, Liu L K. New Ag
+-and Pb
2+-selective electrodes with lariat crown ethers as ionophores. Anal Chim Acta, 2001,432:261-267], pyrazole derivatives [Jain A K, Gupta V K, Singh L P J, et al. A comparative study of Pb
2+selective sensors based on derivatized tetrapyrazole and calix[4] arene receptors. Electrochim Acta, 2006, 51:2547-2553], Calixarene Derivatives [Bhat V S, Ijeri V S, Srivastava A K. Coated wire lead (II) selective potentiometric sensor based on 4-tert-butylcalix[6] arene. Sens Actuators B, 2004, 99:98-105. Wang Hao, Lee's Zhe, Liu Yu. the synthetic and cation selective that lower edge contains heteroatoms cup [4] aromatic hydrocarbons. the Chinese B of section collects: chemistry, 2007, 37 (4): 350-354], derivatives of porphyrin [Lee H K, Song K, Seo H R, et al. Lead (II)-selective electrodes based on tetrakis (2-hydroxy-1-naphthyl) porphyrins:The effect of atropisomers. Sens Actuators B, 2004, 99:323-329] etc.
Be applied to the study on the modification of the macrocyclic compound carrier of high-performance Lead Ion-selective Electrode, mainly concentrate on substituting modification macrocyclic compound being done by the method for chemosynthesis, object is cavity size and the configuration that regulates macrocyclic compound with substituting group, make substituting group can bring into play collaborative complexing together with the cavity of macrocyclic compound carrier, realize the selective complexation to lead ion, avoid other ion interference.But the modification of these macrocyclic compound carriers all needs through numerous and diverse chemosynthesis process and uses a large amount of organic reagents.
Summary of the invention
Object of the present invention is exactly to make in order to solve existing employing chemical modification method the deficiency that Lead Ion-selective Electrode exists, and a kind of organic polycomponent complex carrier Lead Ion-selective Electrode that adopts physical method to make is provided.
The technical solution used in the present invention is as follows:
One, a kind of organic polycomponent complex carrier Lead Ion-selective Electrode, formed by selective membrane, polyvinyl chloride pipe, Ag/AgCl internal reference electrode, internal-filling liquid, electrode end cap and extension line, it is characterized in that described selective membrane is made up of the raw material of following parts by weight proportioning: 1 part of blend carrier, 30～60 parts of Polyvinylchloride powder, 40～80 parts of dibutyl phthalates, 1～5 part of tetraphenylboron sodium.
On the basis of technique scheme, can there is following further optimal technical scheme:
Tetraphenylporphyrin or 18-crown ether-6 and dimethyl sulfide, triphenyl phosphorus, mix composition blend carrier in the parts by weight ratio of 1:1:1;
Or tetraphenylporphyrin mixes composition blend carrier with dimethyl sulfide in the mass fraction ratio of 1:1;
Or tetraphenylporphyrin mixes composition blend carrier with triphenyl phosphorus in the mass fraction ratio of 1:1;
Or tetraphenylporphyrin mixes composition blend carrier with 18-crown ether-6 in the mass fraction ratio of 1:1;
Or tetraphenylporphyrin or 18-crown ether-6 are mixed in the parts by weight ratio of 1:1 with dimethyl sulfide, mix in the parts by weight ratio of 1:1 with triphenyl phosphorus tetraphenylporphyrin or 18-crown ether-6, and above-mentioned two kinds of potpourris are mixed to composition blend carrier in the parts by weight ratio of 1:1 again.
Two, a kind of preparation method of organic polycomponent complex carrier Lead Ion-selective Electrode, make Lead Ion-selective Electrode by selective membrane, polyvinyl chloride pipe, Ag/AgCl internal reference electrode, internal-filling liquid, electrode end cap and extension line, it is characterized in that the preparation of described selective membrane comprises the following steps:
The preparation of a, blend carrier
Tetraphenylporphyrin and dimethyl sulfide, triphenyl phosphorus, mix in the mass fraction ratio of 1:1:1, then adds appropriate tetrahydrofuran, and ultrasonic dispersion, makes blend carrier;
Or tetraphenylporphyrin mixes in the mass fraction ratio of 1:1 with dimethyl sulfide, adds appropriate tetrahydrofuran, and ultrasonic dispersion, makes blend carrier;
Or tetraphenylporphyrin mixes in the mass fraction ratio of 1:1 with triphenyl phosphorus, adds appropriate tetrahydrofuran, and ultrasonic dispersion, makes blend carrier;
Or tetraphenylporphyrin mixes with the mass fraction ratio of 18-crown ether-6 1:1, adds appropriate tetrahydrofuran, and ultrasonic dispersion, makes blend carrier.Make blend carrier;
The preparation of b, lead ion selective membrane
Adopt the raw material of following parts by weight proportioning: 1 part of blend carrier, 30～60 parts of Polyvinylchloride powder, 40～80 parts of dibutyl phthalates, 1～5 part of tetraphenylboron sodium, after the raw material of said ratio is mixed, adds appropriate tetrahydrofuran, ultrasound wave fully heats dispersion, above-mentioned solution is poured into and is bonded in the glass ring that on glass sheet, diameter is 80mm, under room temperature, make naturally to dry after tetrahydrofuran volatilization, make the lead ion selective membrane of organic polycomponent physical blending carrier.
Basic ideas of the present invention are that large cyclisation is closed as calixarenes, tetraphenylporphyrin, 18-crown ether-6 etc., and the organism that contains soft active atomic (O, S, P) is as triphenyl phosphorus, dimethyl sulfide fully mix, and makes physical blending carrier.Then blend carrier, Polyvinylchloride powder, dibutyl phthalate (DBP) and tetraphenylboron sodium are dissolved in tetrahydrofuran, ultrasonic dispersion, solvent evaporates is dry, obtains lead ion selective membrane.O on the one hand, S, P etc. have lone pair electrons, can there is special synergy with macrocyclic compound, due to coverage, the stack of the structure of matter, the size of macrocyclic compound cavity, configuration, rigidity etc. are adjusted on the other hand, thereby change roping capability, susceptibility etc. to lead ion, and change the responding ability to lead ion, the performance of ion-selective electrode is improved.
Finally, make Lead Ion-selective Electrode with selective membrane, Polyvinylchloride (PVC) pipe, Ag/AgCl internal reference electrode, internal-filling liquid, electrode end cap, extension line assembling, this part content belongs to known technology.
The present invention compared with prior art, has significant technical progress, reaches the object of support modification by physical mixed, and the performance of ion-selective electrode is improved.Electrode preparation of the present invention is simple, the particularly preparation of active carrier, avoid numerous and diverse chemosynthesis process and used a large amount of organic reagents, reduce cost, improve efficiency, and electrode good linearity, response are soon, other Cation Interferences is less, stability is high, and can reach 3 months serviceable life, and quantitative and qualitative analysis detection is carried out in the fields such as industrial waste water, biomedicine and food that can be used on.
Accompanying drawing explanation:
Fig. 1 is the structural representation of organic polycomponent complex carrier Lead Ion-selective Electrode, wherein: 1, selective membrane; 2, pvc pipe; 3, Ag/AgCl internal reference electrode; 4, internal-filling liquid; 5, electrode end cap; 6, extension line;
Fig. 2 is this special response curve of energy of each electrode pair lead ion;
Fig. 3 is the graph of a relation of each electrode response current potential and lead ion solution PH.
Embodiment:
Below in conjunction with drawings and Examples, the invention will be further described
It is pure that agents useful for same of the present invention is analysis, and configuration solution all adopts redistilled water.Tetraphenylporphyrin; 18-crown ether-6; Triphenyl phosphorus; Dimethyl sulfide; Dibutyl phthalate (DBP), Chemical Reagent Co., Ltd., Sinopharm Group produces; Polyvinylchloride (PVC) average degree of polymerization 700 ± 50, Dajie Chemical Co., Ltd., Tianjin produces; Tetraphenylboron sodium (NaTPB), Shanghai Qing Xi Chemical Industry Science Co., Ltd produces; Tetrahydrofuran (THF), Wuxi City Ya Sheng chemical industry Chemical Co., Ltd. produces; Plumbi nitras, chemical reagent work of HeFei University of Technology produces; Acetone, chemical reagent work of HeFei University of Technology produces; PHS-2C digital ph, Hangzhou Dong Xing Instrument Ltd. produces; 218 type Ag/AgCl electrodes, Shanghai Precision Scientific Apparatus Co., Ltd produces; 217 type biliquids connect saturated calomel electrode, and Shanghai Lei Ci instrument plant produces; Machinery stopwatch, upper starfish is bored stopwatch company limited and produces; JB-EA type stirrer, Shanghai Precision Scientific Apparatus Co., Ltd produces; FA1604N type electronic balance, Shanghai Precision Scientific Apparatus Co., Ltd produces.
Embodiment mono-: tetraphenylporphyrin one-component is as the preparation (blank) of carrier and film thereof
0.006g tetraphenylporphyrin, is dissolved in 5mL THF, ultrasonic dispersion 5min, then add successively 0.006g NaTPB, 0.2mL DBP, 0.2g PVC powder, intermittently ultrasonic dispersion 10min.Above-mentioned solution is poured into and is bonded in the glass ring that on glass sheet, diameter is 80mm, and under room temperature, 24h dries naturally, obtains pliable and tough and whippy selective membrane.
Embodiment bis-: tetraphenylporphyrin and dimethyl sulfide blend are as the preparation of carrier and film thereof
0.003g tetraphenylporphyrin, 0.003g dimethyl sulfide, is dissolved in 5mL THF, ultrasonic dispersion 5min, then add successively 0.006g NaTPB, 0.2mLDBP, 0.2gPVC powder, intermittently ultrasonic dispersion 10min.Above-mentioned solution is poured into and is bonded in the glass ring that on glass sheet, diameter is 80mm, and under room temperature, 24h dries naturally, obtains pliable and tough and whippy selective membrane.
Embodiment tri-: tetraphenylporphyrin and triphenyl phosphorus blend are as the preparation of carrier and film thereof
0.003g tetraphenylporphyrin, 0.003g triphenyl phosphorus, is dissolved in 5mL THF, ultrasonic dispersion 5min, then add successively 0.006g NaTPB, 0.2mLDBP, 0.2gPVC powder, intermittently ultrasonic dispersion 10min.Above-mentioned solution is poured into and is bonded in the glass ring that on glass sheet, diameter is 80mm, and under room temperature, 24h dries naturally, obtains pliable and tough and whippy selective membrane.
Embodiment tetra-: tetraphenylporphyrin and dimethyl sulfide, triphenyl phosphorus blend are as the preparation of carrier and film thereof
0.002g tetraphenylporphyrin, 0.002g dimethyl sulfide, 0.002g triphenyl phosphorus, is dissolved in 5mL THF, ultrasonic dispersion 5min, then add successively 0.006g NaTPB, 0.2mLDBP, 0.2gPVC powder, intermittently ultrasonic dispersion 10min.Above-mentioned solution is poured into and is bonded in the glass ring that on glass sheet, diameter is 80mm, and under room temperature, 24h dries naturally, obtains pliable and tough and whippy selective membrane.
Embodiment five: tetraphenylporphyrin and 18-crown ether-6 blend are as the preparation of carrier and film thereof
0.003g tetraphenylporphyrin, 0.003g18-crown ether-6, are dissolved in 5mL THF, ultrasonic dispersion 5min, then add successively 0.006g NaTPB, 0.2mLDBP, 0.2gPVC powder, intermittently ultrasonic dispersion 10min.Above-mentioned solution is poured into and is bonded in the glass ring that on glass sheet, diameter is 80mm, and under room temperature, 24h dries naturally, obtains pliable and tough and whippy selective membrane.
The organic polycomponent blend carrier selective membrane being made by above-described embodiment, prepare Lead Ion-selective Electrode:
The PVC powder THF solution that is 5% with mass percent is as bonding agent, lead ion selective membrane is bonded to the lower end of pvc pipe, after drying, in pvc pipe, be filled with the lead nitrate solution of certain volumetric molar concentration as internal-filling liquid, insert Ag/AgCl electrode as internal reference electrode, the upper end cover top electrode end cap of pvc pipe, draws wire, makes the Lead Ion-selective Electrode of organic polycomponent physical blending complex carrier.
The preparation of Dithizone:
Take 3.310g plumbi nitras and be placed in beaker, with redistilled water dissolving, be transferred in 100mL volumetric flask, add redistilled water constant volume, join to obtain 0.1000molL
-1dithizone.The preparation of all the other concentration adopts the preparation of stepwise dilution method.As, pipette the 0.1000molL of 10mL
-1dithizone, in 100mL volumetric flask, adds redistilled water constant volume, shakes up, and joins to obtain 0.01 molL
-1dithizone, stepwise dilution can be joined to obtain solution to 10
-7molL
-1.
The performance test of Lead Ion-selective Electrode:
Measure the electrode performance parameters such as the response curve, response time, PH platform, selectivity of the Lead Ion-selective Electrode of organic polycomponent physical blending complex carrier.
The mensuration of electrode potential
The measurement of current potential is used PHS-2C type PH meter.Outer contrast electrode is that 217 type biliquids connect saturated calomel electrode, and salt bridge is 0.1molL
-1kCl solution.Whole electrode is constructed as follows:
Internal reference electrode (Ag/AgCl) ︱ 10
-2molL
-1the Lead Ion-selective Electrode of the organic polycomponent physical blending of plumbi nitras ︱ complex carrier is surveyed the outer contrast electrode (SCE) of solution ︱ salt bridge ︱ outward with film ︱.
Concrete assay method: it is 10 that solution to be measured adopts concentration
-1～10
-8molL
-1plumbous standard solution.Measure the certain density plumbous standard solution of 30mL in 50mL beaker, membrane electrode is connected with PH meter with outer contrast electrode, PH meter is adjusted to mV shelves, measure from low to high by concentration.Constant agitation speed when measurement.Electrode uses front 10
-3molL
-1in lead nitrate solution, activate 24h hour, test is at room temperature carried out.
Test case 1:
The PVC powder THF solution that is 5% with mass percent, as bonding agent, will, using tetraphenylporphyrin one-component as the obtained film of carrier, stick at the lower end that diameter is the pvc pipe of 16mm, and bonding firmly, is got 3mL10 with syringe
-2molL
-1plumbous mark liquid is made internal-filling liquid, inserts Ag/AgCl electrode as internal reference electrode, covers electrode cap, draws lead-in wire, makes electrode.Electrode uses before with 10
-3molL
-1after plumbous mark liquid activation 24h, with second distillation be washed to potential value stable after, carry out performance test.
Test case 2:
The PVC powder THF solution that is 5% with mass percent is as bonding agent, will, using tetraphenylporphyrin and dimethyl sulfide blend as the obtained film of carrier, stick at the lower end that diameter is the pvc pipe of 16mm, and bonding firmly, is got 3mL10 with syringe
-2molL
-1plumbous mark liquid is made internal-filling liquid, inserts Ag/AgCl electrode as internal reference electrode, covers electrode cap, draws lead-in wire, makes electrode.Electrode uses before with 10
-3molL
-1after plumbous mark liquid activation 24h, with second distillation be washed to potential value stable after, carry out performance test.
Test case 3:
The PVC powder THF solution that is 5% with mass percent is as bonding agent, will, using tetraphenylporphyrin and triphenyl phosphorus blend as the obtained film of carrier, stick at the lower end that diameter is the pvc pipe of 16mm, and bonding firmly, is got 3mL10 with syringe
-2molL
-1plumbous mark liquid is made internal-filling liquid, inserts Ag/AgCl electrode as internal reference electrode, covers electrode cap, draws lead-in wire, makes electrode.Electrode uses before with 10
-3molL
-1after plumbous mark liquid activation 24h, with second distillation be washed to potential value stable after, carry out performance test.
Test case 4:
The PVC powder THF solution that is 5% with mass percent is as bonding agent, will, using tetraphenylporphyrin and dimethyl sulfide, triphenyl phosphorus blend as the obtained film of carrier, stick at the lower end that diameter is the pvc pipe of 16mm, and bonding firmly, is got 3mL10 with syringe
-2molL
-1plumbous mark liquid is made internal-filling liquid, inserts Ag/AgCl electrode as internal reference electrode, covers electrode cap, draws lead-in wire, makes electrode.Electrode uses before with 10
-3molL
-1after plumbous mark liquid activation 24h, with second distillation be washed to potential value stable after, then carry out performance test.
Test case 5:
The PVC powder THF solution that is 5% with mass percent is as bonding agent, will, using tetraphenylporphyrin and 18-crown ether-6 blend as the obtained film of carrier, stick at the lower end that diameter is the pvc pipe of 16mm, and bonding firmly, is got 3mL10 with syringe
-2molL
-1plumbous mark liquid is made internal-filling liquid, inserts Ag/AgCl electrode as internal reference electrode, covers electrode cap, draws lead-in wire, makes electrode.Electrode uses before with 10
-3molL
-1after plumbous mark liquid activation 24h, with second distillation be washed to potential value stable after, then carry out performance test.
Fig. 2 has provided in test case 1-5, and 5 kinds of Different electrodes are to this special response curve of the energy of lead ion, and corresponding electrode performance parameter is provided by table 1.
The Lead Ion-selective Electrode performance parameter of the different films of table 1
From Fig. 2 and table 1, can find out, due to the organism difference of 5 kinds of electrode holder blend, they are not quite similar at aspects such as the range of linearity, slope, detection limit, response times.Along with reducing of plumbum ion concentration in liquid to be measured, the corresponding prolongation of response time of all electrodes, but be 10 at plumbum ion concentration
-7molL
-1liquid to be measured in, test case 4 electrodes still can reach stationary value in 35s.What test case 2-5 presented can be better than test case 1 by Ernest & Whitney response performance, be due in test case 1 only using tetraphenylporphyrin one-component as carrier, and test case 2-5 is using tetraphenylporphyrin and dimethyl sulfide or triphenyl phosphorus or 18-crown ether-6 blend as carrier, wherein dimethyl sulfide, triphenyl phosphorus, 18-crown ether-6 have soft base active atomic O, S, P, O, S, P has lone pair electrons, can there is special complexing synergy with tetraphenylporphyrin, thereby improve roping capability, the susceptibility etc. to lead ion.The blend of dimethyl sulfide, triphenyl phosphorus, 18-crown ether-6 and tetraphenylporphyrin on the other hand, the mutual stack between each material different structure, the size of tetraphenylporphyrin cavity, rigidity etc. change, thereby have improved performance.
Test case 6:
With 1.0 × 10
-3molL
-1lead ion solution is investigated the impact of solution pH value on electrode response current potential, uses HNO
3with NaoH regulator solution pH value.Fig. 3 has provided 1.0 × 10 of test case 1-5
-3molL
-1the graph of a relation of different PH and electrode response current potential in lead ion solution.As seen from Figure 3, within the scope of the PH investigating, the impact of different PH test solution on Lead Ion-selective Electrode performance, each electrode also has different PH platforms.Test case 1-5 is respectively, and 3.1～5.4,3.4～6.4,3.7～6.7,3.4～7.8,2.7～5.8.When the pH value of test solution is in flat roof area separately, the response of electrode remains unchanged substantially, illustrates that the scope of application of PH and plumbum ion concentration are irrelevant.Except this scope, electrode response is changed significantly.Under less PH, the H of high-load
+hinder the further ion-exchange of ion in ion and the solution to be measured in carrier film, caused electrode potential unstable.Under higher PH, OH
-content is higher, and the lead ion that concentration is high is easier to Pb (OH)
+and Pb (OH)
2form exist, cause plumbum ion concentration in solution to diminish, cause that electrode potential is unstable.
Test case 8
Fixing interfering ion concentration method in the mixed solution method of employing IUPAC recommendation is measured electrode and is selected coefficient, and fixing interfering ion concentration is 10
-2molL
-1change plumbum ion concentration, the interference coefficient of determination part segregant, the results are shown in Table 2.
The selection coefficient of the various interfering ions of table 2
Table 2 result shows, in table, the selection coefficient of all interfering ions is all less than 1, illustrate that this Lead Ion-selective Electrode has good selectivity to ion, but every kind of interfering ion also has very big difference to the annoyance level of lead ion, the annoyance level being subject to specific to test case 4 is Ag
+> Na
+> Fe
3+> Ca
2+> Cu
2+> Hg
2+.Owing to containing soft base active atomic O, S, P is organic to add, and test case 2-5 all has increase in various degree to the antijamming capability of interfering ion, and wherein test case 2 is to Hg
2+resistivity obviously improve.
Only the present invention will be described for above-described embodiment, do not form the restriction to claim scope, and those skilled in the art can conceivable other substantial equivalence means, all within the scope of claim of the present invention.
Claims (1)
1. a preparation method for organic polycomponent complex carrier Lead Ion-selective Electrode, comprises preparation blend carrier and prepares selective membrane step, it is characterized in that the preparation of blend carrier and selective membrane comprises the following steps:
The preparation of a, blend carrier
Adopt the raw material of following parts by weight proportioning: 1-2 parts of tetraphenylporphyrins or 18-crown ether-6,1 part of dimethyl sulfide, mixes the raw material of above-mentioned mass fraction proportioning and adds appropriate tetrahydrofuran, and ultrasonic dispersion makes blend carrier;
Or 1-2 parts of tetraphenylporphyrins or 18-crown ether-6,1 part of triphenyl phosphorus, mixes the raw material of above-mentioned mass fraction proportioning and adds appropriate tetrahydrofuran, and ultrasonic dispersion makes blend carrier;
Or 1 part of tetraphenylporphyrin or 18-crown ether-6,1 part of dimethyl sulfide, mixes the raw material of above-mentioned mass fraction proportioning and adds appropriate tetrahydrofuran, and ultrasonic dispersion makes blend carrier;
Or adopt the raw material of following parts by weight proportioning: 1-2 parts of tetraphenylporphyrins or 18-crown ether-6,1 part of dimethyl sulfide, 1 part of triphenyl phosphorus, the raw material of above-mentioned parts by weight proportioning is mixed and add appropriate tetrahydrofuran, fully mix with ultrasound wave, volatilization dry tetrahydrofuran, makes blend carrier;
Or 1 part of tetraphenylporphyrin, 1 part of 18-crown ether-6, mixes the raw material of above-mentioned mass fraction proportioning and adds appropriate tetrahydrofuran, and ultrasonic dispersion makes blend carrier;
The preparation of b, lead ion selective membrane
Adopt the raw material of following parts by weight proportioning: 1 part of blend carrier, 30～60 parts of Polyvinylchloride powder, 40～80 parts of dibutyl phthalates, 1～5 part of tetraphenylboron sodium, after the raw material of said ratio is mixed, adds appropriate tetrahydrofuran, ultrasound wave fully heats dispersion, above-mentioned solution is poured into and is bonded in the glass ring that on glass sheet, diameter is 80mm, under room temperature, make naturally to dry after tetrahydrofuran volatilization, make lead ion selective membrane.
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