CN101308113B - Lead ion selective electrode film using poly-1-aminoanthraquinone as carrier, its preparation method and uses thereof - Google Patents
Lead ion selective electrode film using poly-1-aminoanthraquinone as carrier, its preparation method and uses thereof Download PDFInfo
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- CN101308113B CN101308113B CN2008100329704A CN200810032970A CN101308113B CN 101308113 B CN101308113 B CN 101308113B CN 2008100329704 A CN2008100329704 A CN 2008100329704A CN 200810032970 A CN200810032970 A CN 200810032970A CN 101308113 B CN101308113 B CN 101308113B
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Abstract
The invention discloses a membrane used for a lead ion selective electrode and taking a poly 1-aminoanthraquinone as a carrier, which is characterized in that: the membrane comprises poly 1-aminoanthraquinone, polyvinyl chloride and di-n-octyl phthalate. The invention also discloses a process for preparing the membrane used for the lead ion selective electrode and taking the poly 1-aminoanthraquinone as the carrier as well as purposes thereof.
Description
Technical field
The present invention relates to a kind of is lead ion selection electrode film, the Its Preparation Method And Use of carrier with the poly-1-aminoanthraquinone.
Background technology
(ion-selective electrode is a kind of electrochemical sensing body ISE) to ion-selective electrode, is the important component part of potentiometric analysis system.Characteristics such as based on the analytical technology of ion-selective electrode is to utilize the relation of electrode potential and ion activity to realize detection to ion, and it is good that this technology has selectivity, highly sensitive, and analysis speed is fast, and cost is low, and analytic target is extensive, and amount of samples is few.Along with the membrane material of electrode and updating and reforming of manufacturing technology, the ion-selective electrode analysis technology has been widely used in fields such as environment measuring, industrial flow control, clinical medicine, Pharmaceutical Analysis.
Along with fast development of modern industry, many heavy metal ion severe contaminations environment, heavy metal ion is difficult to be degraded by microorganisms, and can hide for a long time to enter plant, animal body and even human body in water body and soil and with food chain, in human body, accumulate, be detrimental to health.Therefore the detection to heavy metal ion seems particularly important.The main method that detects heavy metal ion has spectrophotometric method, atomic absorption method, stripping voltammetry, polarography, inductively coupled plasma mass spectroscopy etc.But there is the instrument costliness in these methods, operates shortcomings such as loaded down with trivial details, and are difficult to realize the on-line monitoring of heavy metal ion.And ion selective electrode method is simple to operate, cost is low, analysis speed is fast, is easy to robotization, particularly very suitable open-air the analysis and an automatic continuous detecting.Therefore, research seems significant to the ion-selective electrode that heavy metal ion has detecting function.
The research major part of counterweight Metal Ion Selective Electrode electrode concentrates on the electrode based on Polyvinylchloride (PVC) film both at home and abroad, and the key of pvc membrane electrode is to select suitable ionophore for use, realizes surveying according to the selectivity of different carriers to metallic ion.The neutral carrier that comprises thioether, crown ether, calixarenes etc. has obtained extensive studies, investigative range is wideer, detection limit is lower in order to develop, response speed ion-selective electrode faster, and the researcher is still seeking the carrier mass that heavy metal ion is had better choice.Discovering in recent years, some novel conducting polymers have stronger and the ability heavy metal ion complexing, the particularly polymkeric substance of some aromatic diamines classes.
Summary of the invention
The objective of the invention is in order to solve deficiency of the prior art, providing a kind of is lead ion selection electrode film, the Its Preparation Method And Use of carrier with the poly-1-aminoanthraquinone.
With the poly-1-aminoanthraquinone is the lead ion selection electrode film of carrier, it is characterized in that, comprises poly-1-aminoanthraquinone, Polyvinylchloride and di-n-octyl phthalate.
Wherein, the weight ratio of poly-1-aminoanthraquinone, Polyvinylchloride and di-n-octyl phthalate is 1: (10～50): (30～100).
Wherein, also comprise the negative ion eliminant.
Wherein, the weight ratio of poly-1-aminoanthraquinone, Polyvinylchloride, di-n-octyl phthalate and negative ion eliminant is 1: (10～50): (30～100): (1～10).
Wherein, described negative ion eliminant is selected from tetraphenylboron sodium, potassium tetraphenylborate, four (4-chlorobenzene) boronation potassium etc.
Preferably, described film thickness is 0.07mm～0.30mm.
Preparation is that the lead ion of carrier is selected the method for electrode with film with the poly-1-aminoanthraquinone, it is characterized in that, poly-1-aminoanthraquinone, Polyvinylchloride and di-n-octyl phthalate mixing are placed organic solvent, fully disperse, after the solvent evaporates, promptly making with the poly-1-aminoanthraquinone is the lead ion selection electrode film of carrier.
Wherein, described organic solvent is selected from tetrahydrofuran, chloroform, methylene chloride, acetone etc.
Wherein, the weight ratio of poly-1-aminoanthraquinone, Polyvinylchloride and di-n-octyl phthalate is 1: (10～50): (30～100).
Wherein, also comprise the negative ion eliminant.
Wherein, the weight ratio of poly-1-aminoanthraquinone, Polyvinylchloride, di-n-octyl phthalate and negative ion eliminant is 1: (10～50): (30～100): (1～10).
Wherein, described negative ion eliminant is selected from tetraphenylboron sodium, potassium tetraphenylborate or four (4-chlorobenzene) boronation potassium.
Described is that the lead ion of carrier selects electrode to be used for surveying the solution plumbum ion concentration with film with the poly-1-aminoanthraquinone.
Described is that the lead ion of carrier selects electrode to be used for surveying the solution plumbum ion concentration with film with the poly-1-aminoanthraquinone, it is characterized in that, with claim 1-5 described be that the lead ion of carrier selects electrode to be used to make exploring electrode with film with the poly-1-aminoanthraquinone, whole exploring electrode is constructed as follows:
Internal reference electrode (Ag/AgCl) | 0.1molL
-1Lead nitrate solution | with the poly-1-aminoanthraquinone is the lead ion selection electrode film of carrier | solution to be measured | salt bridge | outer contrast electrode (SCE)
Measure the standard solution that 5-10 organizes known plumbum ion concentration at first respectively, according to measurement result, with electrode response current potential EMF is ordinate, with lg[C] be horizontal ordinate, make EMF and lg[C] relation curve, promptly get working curve, when measuring the solution of unknown plumbum ion concentration, measure its response current potential EMF value, can know plumbum ion concentration according to its relation curve; Wherein, lg[C] in, C represents plumbum ion concentration.
Wherein, the pH value of solution to be measured is 2.8～5.2.
Among the present invention, PAAQ is a poly-1-aminoanthraquinone, and PVC is a Polyvinylchloride; DOP is a di-n-octyl phthalate; THF is a tetrahydrofuran; NaTPB is a tetraphenylboron sodium; EMF in the accompanying drawing is the electrode response current potential that records.
Among the present invention is the lead ion selection electrode film of carrier with the poly-1-aminoanthraquinone, and its detection performance is led over the domestic electrode of reporting, also has certain competitive edge with the electrode of reporting in the world, is embodied in:
(1) selected ionophore poly-1-aminoanthraquinone is to make by simple chemical oxidation synthetic method, and equipment is simple, the productive rate height, and 1-amino anthraquinones monomer belongs to domestic common chemical products, the source is abundant, and is cheap, makes the electrode of being developed have lower cost.
(2) lead ion is had this special response of good energy, have the range of linearity (2.5 * 10 of broad
-6-1.0 * 10
-1MolL
-1) and lower detection limit (7.8 * 10
-7MolL
-1), and have this special response slope of energy that meets with theoretical value.
(3) have the response speed that is exceedingly fast, the response time only is 12s, can realize the fast detecting to lead ion.
(4) has good selectivity, alkali metal ion (Na
+, K
+Deng) and alkaline-earth metal ions (Ba
2+, Ca
2+Deng) electrode is not caused interference substantially, interference coefficient all is far smaller than 1.
The lead ion that with the poly-1-aminoanthraquinone is carrier selects electrode to have the range of linearity of broad with film, lower detection limit and response speed faster, and this electrode has good selectivity simultaneously, is subjected to other cationic interference less.The synthetic method of adding the carrier mass poly-1-aminoanthraquinone is simple, raw material sources are extensive, cost is low.Make that what developed is that the lead ion of carrier selects electrode to have bigger competitive edge in similar electrode with the poly-1-aminoanthraquinone, has broad application prospects.
Description of drawings
Fig. 1 is the influence of the consumption of carrier PAAQ to the potential response of electrode;
Fig. 2 consists of PAAQ: PVC: DOP: NaTPB=1: the thickness of 33: 66: 1 ion-selective membrane is to the influence of electrode potential response;
Fig. 3 is the relation of the pH value of the response current potential of electrode and three kinds of concentration lead ion solution;
Fig. 4 is for consisting of PAAQ: PVC: DOP: NaTPB=1: 33: 66: 1, thickness was the response time of the membrane electrode of 0.09mm
Fig. 5 membrane electrode is 1 * 10 in concentration
-3MolL
-1The various interfering ions response current potential under existing;
Fig. 6 is with 1.00 * 10
-3MolL
-1EDTA titration 1.00 * 10
-3MolL
-1Pb (NO
3)
2The potentiometric titration curve of solution;
Embodiment
It is pure that the used reagent of the present invention is analysis, and configuration solution all adopts the deionized water of distillation once more.The 1-amino anthraquinones, ammonium persulfate, Shanghai green grass or young crops is analysed Chemical Industry Science Co., Ltd; Polyvinylchloride (PVC), ShanghaiChlorine and Alkali Chemical Co Ltd; Di-n-octyl phthalate (DOP), Chemical Reagent Co., Ltd., Sinopharm Group; Tetrahydrofuran (THF), Shanghai Ling Feng chemical reagent company limited; Tetraphenylboron sodium (NaTPB), Chemical Reagent Co., Ltd., Sinopharm Group; Plumbi nitras, Chemical Reagent Co., Ltd., Sinopharm Group.
The preparation of plumbi nitras standard solution
Take by weighing the 3.31g plumbi nitras and place beaker,, pour in the volumetric flask of 100mL, increase the weight of to boil off ionized water to graticule with heavily boiling off ionized water dissolving, join 0.1molL
-1Lead nitrate solution.The configuration of stepwise dilution method is adopted in the plumbi nitras standard solution preparation of other concentration.As pipette the 0.1molL of 10mL
-1Lead nitrate solution increases the weight of to boil off ionized water to graticule in the volumetric flask of 100mL, can join 0.01molL
-1Lead nitrate solution.The configurable solution to 10 of stepwise dilution
-8MolL
-1
The preparation of carrier poly-1-aminoanthraquinone
Adopt the chemical oxidation synthetic method to prepare poly-1-aminoanthraquinone (PAAQ).Take by weighing 2mmol (446mg) 1-amino anthraquinones monomer, put into the 100ml beaker, add the 40ml acetonitrile, and pipette perchloric acid with transfer pipet and splash in the beaker, making the concentration of perchloric acid among acetonitrile solution is 0.05mol/L.Accurately take by weighing 2mmol (456mg) ammonium persulfate as oxygenant with analytical balance in addition, be dissolved among the 0.75mL deionized water, two beakers that fill monomer solution and oxygenant are all placed 20 ℃ water bath with thermostatic control.Then the speed of oxidizing agent solution with 1/3 seconds is splashed in the monomer solution, simultaneously monomer will stir on magnetic stirring apparatus, drip off oxygenant after, isothermal reaction 24h under magnetic stirrer.Reaction is centrifugal with system after finishing, and adopts absolute ethanol washing afterwards in 50 ℃ of oven dry down solid product.
Take by weighing poly-1-aminoanthraquinone (PAAQ) 8mg respectively, Polyvinylchloride (PVC) 200mg, di-n-octyl phthalate (DOP) 400mg, tetraphenylboron sodium (NaTPB) 8mg, these four kinds of reagent are added in the beaker, and add the 5mL tetrahydrofuran, intermittently ultrasonic dissolution is 1 hour.Then mixed liquor is poured on flat on glassly, placed 24 hours, treat that tetrahydrofuran volatilizees fully after, obtain a tough and whippy film, film consist of PAAQ: PVC: DOP: NaTPB=1: 25: 50: 1, the thickness of film was 0.16mm.The film that makes is downcut the disk that a diameter is about 16mm, and sticking at internal diameter with epoxy resin is that 13mm, external diameter are the pvc pipe end of 15mm.In pipe, fill 0.1molL
-1Pb (NO3) 2 reference solutions, and insert the Ag/AgCl electrode and do internal reference electrode.Electrode is before using, with 10
-3MolL
-1Lead nitrate solution activation 12h, afterwards with heavily boiling off till ionized water is washed till potential value and stablizes.
Take by weighing poly-1-aminoanthraquinone (PAAQ) 6.06mg respectively, Polyvinylchloride (PVC) 200mg, di-n-octyl phthalate (DOP) 400mg, tetraphenylboron sodium (NaTPB) 6.06mg, these four kinds of reagent are added in the beaker, and add the 5mL tetrahydrofuran, intermittently ultrasonic dissolution is 1 hour.Then mixed liquor is poured on flat on glassly, placed 24 hours, treat that tetrahydrofuran volatilizees fully after, obtain a tough and whippy film, film consist of PAAQ: PVC: DOP: NaTPB=1: 33: 66: 1, the thickness of film was 0.16mm.The film that makes is downcut the disk that a diameter is about 16mm, and sticking at internal diameter with epoxy resin is that 13mm, external diameter are the pvc pipe end of 15mm.In pipe, fill 0.1molL
-1Pb (NO
3)
2Reference solution, and insert the Ag/AgCl electrode and do internal reference electrode.Electrode is before using, with 10
-3MolL
-1Lead nitrate solution activation 12h, afterwards with heavily boiling off till ionized water is washed till potential value and stablizes.
Take by weighing poly-1-aminoanthraquinone (PAAQ) 4mg respectively, Polyvinylchloride (PVC) 200mg, di-n-octyl phthalate (DOP) 400mg, tetraphenylboron sodium (NaTPB) 4mg, these four kinds of reagent are added in the beaker, and add the 5mL tetrahydrofuran, intermittently ultrasonic dissolution is 1 hour.Then mixed liquor is poured on flat on glassly, placed 24 hours, treat that tetrahydrofuran volatilizees fully after, obtain a tough and whippy film, film consist of PAAQ: PVC: DOP: NaTPB=1: 50: 100: 1, the thickness of film was 0.16mm.The film that makes is downcut the disk that a diameter is about 16mm, and sticking at internal diameter with epoxy resin is that 13mm, external diameter are the pvc pipe end of 15mm.In pipe, fill 0.1molL
-1Pb (NO
3)
2Reference solution, and insert the Ag/AgCl electrode and do internal reference electrode.Electrode is before using, with 10
-3MolL
-1Lead nitrate solution activation 12h, afterwards with heavily boiling off till ionized water is washed till potential value and stablizes.
Take by weighing poly-1-aminoanthraquinone (PAAQ) 6.06mg respectively, Polyvinylchloride (PVC) 200mg, di-n-octyl phthalate (DOP) 400mg, tetraphenylboron sodium (NaTPB) 6.06mg, these four kinds of reagent are added in the beaker, and add the 5mL tetrahydrofuran, intermittently ultrasonic dissolution is 2 hours.Then mixed liquor is poured on flat on glassly, placed 24 hours, treat that tetrahydrofuran volatilizees fully after, obtain a tough and whippy film, the thickness of film is 0.22mm.The film that makes is downcut the disk that a diameter is about 16mm, and sticking at internal diameter with epoxy resin is that 13mm, external diameter are the pvc pipe end of 15mm.In pipe, fill 0.1molL
-1Pb (NO
3)
2Reference solution, and insert the Ag/AgCl electrode and do internal reference electrode.Electrode is before using, with 10
-3MolL
-1Lead nitrate solution activation 12h, afterwards with heavily boiling off till ionized water is washed till potential value and stablizes.
Take by weighing poly-1-aminoanthraquinone (PAAQ) 6.06mg respectively, Polyvinylchloride (PVC) 200mg, di-n-octyl phthalate (DOP) 400mg, tetraphenylboron sodium (NaTPB) 6.06mg, these four kinds of reagent are added in the beaker, and add the 5mL tetrahydrofuran, intermittently ultrasonic dissolution is 1 hour.Then mixed liquor is poured on flat on glassly, placed 24 hours, treat that tetrahydrofuran volatilizees fully after, obtain a tough and whippy film, the thickness of film is 0.16mm.The film that makes is downcut the disk that a diameter is about 16mm, and sticking at internal diameter with epoxy resin is that 13mm, external diameter are the pvc pipe end of 15mm.In pipe, fill 0.1molL
-1Pb (NO
3)
2Reference solution, and insert the Ag/AgCl electrode and do internal reference electrode.Electrode is before using, with 10
-3MolL
-1Lead nitrate solution activation 12h, afterwards with heavily boiling off till ionized water is washed till potential value and stablizes.
Take by weighing poly-1-aminoanthraquinone (PAAQ) 6.06mg respectively, Polyvinylchloride (PVC) 200mg, di-n-octyl phthalate (DOP) 400mg, tetraphenylboron sodium (NaTPB) 6.06mg, these four kinds of reagent are added in the beaker, and add the 5mL tetrahydrofuran, intermittently ultrasonic dissolution is 0.5 hour.Then mixed liquor is poured on flat on glassly, placed 24 hours, treat that tetrahydrofuran volatilizees fully after, obtain a tough and whippy film, the thickness of film is 0.09mm.The film that makes is downcut the disk that a diameter is about 16mm, and sticking at internal diameter with epoxy resin is that 13mm, external diameter are the pvc pipe end of 15mm.In pipe, fill 0.1molL
-1Pb (NO
3)
2Reference solution, and insert the Ag/AgCl electrode and do internal reference electrode.Electrode is before using, with 10
-3MolL
-1Lead nitrate solution activation 12h, afterwards with heavily boiling off till ionized water is washed till potential value and stablizes.
Tetraphenylboron sodium in the foregoing description can replace with potassium tetraphenylborate or four (4-chlorobenzene) boronation potassio; Tetrahydrofuran can use replacements such as chloroform, methylene chloride or acetone.
The mensuration of current potential
The measurement of current potential is used and is gone up the PHS-3C type pH meter that Haikang instrument Instr Ltd. produces.Outer contrast electrode is that 217 type biliquids connect saturated calomel electrode, and salt bridge is 0.1molL
-1KCl solution.Entire electrode is constructed as follows: internal reference electrode (Ag/AgCl) | 0.1molL
-1Lead nitrate solution | with the poly-1-aminoanthraquinone is the lead ion selection electrode film of carrier | solution to be measured | salt bridge | outer contrast electrode (SCE)
Concrete method of testing: it is 10 that solution to be measured adopts concentration
-8-10
-1MolL
-1Pb (NO
3)
2Standard solution.Measure the certain density Pb (NO of 20mL
3)
2Solution links to each other with membrane electrode outer contrast electrode in beaker with pH meter, pH meter is transferred to the emf measurement shelves.Outer contrast electrode and membrane electrode are placed solution to be measured, treat to write down when potential response is stablized stable potential value.
During the pH value scope of application of inspecting electrode, adopt HNO
3With NaOH the pH value of solution is regulated.
During response time of inspecting electrode, the time of recording film electrode when touching current potential and reach balance with variable concentrations solution to be measured is the response time of electrode.
Embodiment 7-9
Study electrode with the influence of film by the consumption that changes carrier PAAQ to electrode performance.Fig. 1 is the membrane electrode that the makes potential response curve to lead ion under three kinds of different amounts of carrier PAAQ, the corresponding electrode performance parameter sees Table 1.As can be seen, the membrane electrode under three kinds of carrier consumptions all shows preferably lead ion can this special response, but it selects performance parameter of electrode that bigger difference is then arranged as lead ion.Wherein, the carrier consumption mediates, and consists of PAAQ: PVC: DOP: NaTPB=1: 33: 66: 1 electrode has shown this special response of best energy, and its slope is 28.1mVdecade
-1, near this special slope theoretical value 29.6mVdecade of energy
-1, range of linearity broad is 4.0 * 10
-6-1.0 * 10
-1MolL
-1, detection limit can reach 1.86 * 10
-6MolL
-1
Table 1 is the performance parameter that the lead ion under the different films of carrier are formed is selected electrode with PAAQ
| PAAQ: PVC: DOP: NaTPB (weight ratio) | The range of linearity/(molL -1) | Linear equation | Slope/(mVdecade -1) | Detection limit/(molL -1) | Response time/ |
| 1∶25∶50∶1 | 1.0×10 -5-1.0×10 -1 | E＝129.6-26.71g[C] | 26.7 | 3.29×10 -6 | 16 |
| 1∶50∶100∶1 | 1.0×10 -5-2.4×10 -2 | E＝112.6-27.91g[C] | 27.9 | 2.92×10 -6 | 17 |
| 1∶33∶66∶1 | 4.0×10 -6-1.0×10 -1 | E＝126.1-28.1lg[C] | 28.1 | 1.86×10 -6 | 14 |
Embodiment 10-12
Selective membrane consist of PAAQ: PVC: DOP: NaTPB=1: 33: 66: 1, see Fig. 2 with the potential response of the different prepared electrode of sensitive membrane of three kinds of thickness, the corresponding electrode performance parameter is listed in table 2.Discovery is along with the reduction of sensitive membrane thickness, and each performance parameter of electrode also improves thereupon, and sensitive membrane thickness is that this special response slope of energy of the electrode of 0.09mm is 28.9mVdecade
-1, this special slope theoretical value of the most approaching energy.The range of linearity of its detection is 2.5 * 10
-6-1.0 * 10
-1MolL
-1, be that the electrode of 0.22mm is compared with sensitive membrane thickness, the range of linearity has been widened order of magnitude nearly, and its detection limit also is the minimum in all electrodes, can reach 7.76 * 10
-7MolL
-1
Table 2 different-thickness consist of PAAQ: PVC: DOP: NaTPB=1: 33: 66: 1 lead ion is selected the performance parameter of electrode with film
| Thickness/mm | The range of linearity/(molL -1) | Linear equation | Slope/(mVdecade -1) | Detection limit/(molL -1) | Response time/s |
| 0.22 | 1.0×10 -5-1.0×10 -1 | E＝120.5-28.7lg[C] | 28.7 | 4.47×10 -6 | 15 |
| 0.16 | 4.0×10 -6-1.0×10 -1 | E＝126.1-28.1lg[C] | 28.1 | 1.86×10 -6 | 14 |
| 0.09 | 2.5×10 -6-1.0×10 -1 | E＝132.5-28.9lg[C] | 28.9 | 7.76× |
12 |
Embodiment 13-15
Consist of PAAQ: PVC: DOP: NaTPB=1: 33: 66: 1, thickness be the membrane electrode of 0.09mm in three kinds of lead at different concentrations solions potential response and the relation of pH value see Fig. 3.The pH value was less than 2.8 o'clock, current potential fluctuates bigger along with the variation of pH value, the pH value was greater than 5.2 o'clock, current potential fluctuates bigger along with the variation of pH value, the pH usable range of this electrode is 2.8-5.2, the response current potential of electrode is not subjected to the influence of pH value in this scope, exceeds this scope, and current potential fluctuates along with the variation of pH value.The pH value mainly shows both ways the influence of electrode, and the one, to the influence of lead ion hydrolyzed state, then be to influence the complexing behavior of carrier in addition to lead ion.When the pH value is higher, Pb
2+Easily and OH
-In conjunction with forming Pb (OH)
+And Pb (OH)
2, cause Pb free in the solution
2+Density loss, thus the variation of current potential caused; When the pH value is low, the H of high concentration
+Easily that the N in the carrier poly-1-aminoanthraquinone is protonated, in addition with the Pb of complexing
2+Ion-exchange takes place cause desorption, these have all reduced the complexing power of carrier to lead ion, cause the variation of electrode response current potential.
Embodiment 16-18
Consist of PAAQ: PVC: DOP: NaTPB=1: 33: 66: 1, thickness was that potential response and the time relation of membrane electrode in three kinds of different plumbum ion concentrations of 0.09mm seen Fig. 4.As can be seen, at three kinds of different Pb
2+Under the concentration, the response current potential of electrode can reach stable in 12s, and response speed is very fast, and the lead ion of reporting near document is selected the fastest response speed of electrode.Because poly-1-aminoanthraquinone has the ability of quick complexing lead ion, its intrinsic conductivity helps the transmission of electric charge in the film in addition, has reduced the film internal resistance, thereby has given electrode very fast response speed.Electrode can use more than 2 months at least and its performance parameter does not change substantially, its range of linearity, can this special response slope etc. still keeps with originally consistent.
Embodiment 19
Selectivity is to weigh the important indicator of ion-selective electrode.Desirable ion-selective electrode should be only have a kind of specific ion can this special response, but in fact other coexisting ions in the detected solution can produce electrode response and disturb.Usually use potential selectivity coefficient K
I, j PotWeigh the selectivity of electrode, it is defined as when other test conditions are identical, can produce the ion activity α to be measured of same potential
iWith the interfering ion activity alpha
jRatio, promptly
K
I, j PotRepresented that interfering ion is to the contribution of ion-selective electrode current potential in the mixed solution, its value is more little, represents that the selectivity of this electrode is good more.The method of measuring potentiometric selectivity coefficient has separate solution method (SSM) and fixed interference method (FIM), separate solution method is generally measured solution that only contains main ion and the solution that only contains interfering ion respectively by electrode, and tries to achieve potential selectivity coefficient according to the concentration ratio of equipotential response point main ion and interfering ion; Fixed interference method then is under the concentration of fixing interfering ion, and the concentration that changes main ion is measured, and tries to achieve potential selectivity coefficient according to the detection lower limit and the fixing interfering ion concentration of contrast of electrode pair main ion.Because separate solution method only is and can be suitable under situation of this spy's response in the electrode strictness, can not reflect that electrode is applied to interfering ion and the actual conditions of ion coexist to be measured in same test solution, therefore normal employing fixed interference method is measured potentiometric selectivity coefficient.
The present invention promptly adopts fixed interference method to measure the selection coefficient of electrode, and the concentration fixed of interfering ion is 1 * 10
-3MolL
-1The electrode of studying in the presence of various interfering ions potential response and the relation of plumbum ion concentration see Fig. 5, the potentiometric selectivity coefficient that is calculated sees Table 3.As can be seen from Table 3, alkali metal ion (Na
+, K
+Deng) and alkaline-earth metal ions (Ba
2+, Ca
2+Deng) electrode is not caused interference substantially, interference coefficient is all 8 * 10
-3Below, be far smaller than 1, illustrate that what studied is that the ion-selective membrane electrode pair lead ion of carrier has good selectivity with PAAQ.
(concentration fixed of interfering ion is 1 * 10 to the potentiometric selectivity coefficient of the various interfering ions of table 3 electrode pair
-3MolL
-1)
| Interfering ion | Potentiometric selectivity coefficient KP b2+，B POT |
| NH 4 + | 7.59×10 -3 |
| Na + | 7.18×10 -3 |
| K + | 4.27×10 -3 |
| Ba 2+ | 3.55×10 -3 |
| Ca 2+ | 3.09×10 -3 |
Selective membrane consists of PAAQ: PVC: DOP: NaTPB=1: 33: 66: 1, thickness was the electrode of 0.09mm, used as the indicator electrode of EDTA potentiometric titration lead ion.With 1.00 * 10
-3MolL
-1EDTA titration 10.00mL1.00 * 10
-3MolL
-1Pb (NO
3)
2Standard solution.Titration curve as shown in Figure 6, potentiometric titration curve does not demonstrate the S type of standard, this may be since EDTA solution in Na
+Disturb caused.Some lead ions of being reported in the document are selected electrode, and when being used as the indicator electrode of EDTA potentiometric titration lead ion, its potentiometric titration curve shows the rule similar to Fig. 6; And, from Fig. 6, still can observe Pb
2+The sudden change position of the corresponding chemical stoichiometric point of-EDTA complex compound, this has shown to be the indicator electrode that the lead ion selective membrane electrode of carrier can be used for the lead ion potentiometric titration with PAAQ.
The foregoing description only is used for that the present invention will be described, does not constitute the restriction to the claim scope, and other substantial equivalence means that it may occur to persons skilled in the art that are all in claim scope of the present invention.
Claims (11)
1. the lead ion that with the poly-1-aminoanthraquinone is carrier is selected the electrode film, it is characterized in that, comprise poly-1-aminoanthraquinone, Polyvinylchloride and di-n-octyl phthalate, the weight ratio of poly-1-aminoanthraquinone, Polyvinylchloride and di-n-octyl phthalate is 1: (10～50): (30～100), described is that the lead ion of carrier selects electrode to adopt following method to make with film with the poly-1-aminoanthraquinone: poly-1-aminoanthraquinone, Polyvinylchloride and di-n-octyl phthalate are mixed placing organic solvent, fully disperse, make after the solvent evaporates.
2. according to claim 1 is the lead ion selection electrode film of carrier with the poly-1-aminoanthraquinone, it is characterized in that also comprise the negative ion eliminant, described negative ion eliminant is selected from tetraphenylboron sodium, potassium tetraphenylborate, four (4-chlorobenzene) boronation potassium.
3. according to claim 2 is the lead ion selection electrode film of carrier with the poly-1-aminoanthraquinone, it is characterized in that the weight ratio of poly-1-aminoanthraquinone, Polyvinylchloride, di-n-octyl phthalate and negative ion eliminant is 1: (10～50): (30～100): (1～10).
4. described according to the arbitrary claim of claim 1-3 is the lead ion selection electrode film of carrier with the poly-1-aminoanthraquinone, it is characterized in that described film thickness is 0.07mm～0.30mm.
5. preparation is the method for the lead ion selection electrode of carrier with film with the poly-1-aminoanthraquinone, it is characterized in that, poly-1-aminoanthraquinone, Polyvinylchloride and di-n-octyl phthalate mixing are placed organic solvent, fully disperse, after the solvent evaporates, promptly making with the poly-1-aminoanthraquinone is the lead ion selection electrode film of carrier, and the weight ratio of poly-1-aminoanthraquinone, Polyvinylchloride and di-n-octyl phthalate is 1: (10～50): (30～100).
6. preparation according to claim 5 is that the lead ion of carrier is selected the method for electrode with film with the poly-1-aminoanthraquinone, it is characterized in that described organic solvent is selected from tetrahydrofuran, chloroform, methylene chloride, acetone.
7. preparation according to claim 5 is that the lead ion of carrier is selected the method for electrode with film with the poly-1-aminoanthraquinone, it is characterized in that, also add the negative ion eliminant, described negative ion eliminant is selected from tetraphenylboron sodium, potassium tetraphenylborate, four (4-chlorobenzene) boronation potassium.
8. preparation according to claim 7 is that the lead ion of carrier is selected the method for electrode with film with the poly-1-aminoanthraquinone, it is characterized in that the weight ratio of poly-1-aminoanthraquinone, Polyvinylchloride, di-n-octyl phthalate and negative ion eliminant is 1: (10～50): (30～100): (1～10).
Claim 1-4 arbitrary described be that the lead ion of carrier selects electrode to be used for surveying the solution plumbum ion concentration with film with the poly-1-aminoanthraquinone.
10. claim 9 is described is that the lead ion of carrier selects electrode to be used for surveying the solution plumbum ion concentration with film with the poly-1-aminoanthraquinone, it is characterized in that, comprise step: with claim 1-4 arbitrary described be that the lead ion of carrier selects electrode to be used to make exploring electrode with film with the poly-1-aminoanthraquinone, whole exploring electrode is constructed as follows:
Internal reference electrode Ag/AgCl|0.1molL
-1Lead nitrate solution | with the poly-1-aminoanthraquinone is the lead ion selection electrode film of carrier | solution to be measured | salt bridge | outer contrast electrode SCE
Measure the standard solution that 5-10 organizes known plumbum ion concentration at first respectively, according to measurement result, with electrode response current potential EMF is ordinate, with lg[C] be horizontal ordinate, make EMF and lg[C] relation curve, promptly get working curve, when measuring the solution of unknown plumbum ion concentration, measure its response current potential EMF value, can know plumbum ion concentration according to its relation curve; Wherein, lg[C] in, C represents plumbum ion concentration.
11. according to claim 9 or 10 described be that the lead ion of carrier selects electrode to be used to survey plumbum ion concentration with film with the poly-1-aminoanthraquinone, it is characterized in that the pH value of solution to be measured is 2.8～5.2.
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