CN101532982B - Preparation method of an ion selective electrode capable of measuring copper (II) in waste water - Google Patents
Preparation method of an ion selective electrode capable of measuring copper (II) in waste water Download PDFInfo
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- CN101532982B CN101532982B CN200910113972A CN200910113972A CN101532982B CN 101532982 B CN101532982 B CN 101532982B CN 200910113972 A CN200910113972 A CN 200910113972A CN 200910113972 A CN200910113972 A CN 200910113972A CN 101532982 B CN101532982 B CN 101532982B
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- phenylenediamine
- salicylidene
- schiff bases
- waste water
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Abstract
The invention provides a preparation method of an ion selective electrode capable of measuring copper (II) in waste water. Schiff bases derived from salicylic aldehyde and o-phenylendiamine is used as the neutral carrier and mixed with carbon powder and liquid paraffin is used as adhesive, thus the nernst response copper (II) ion selective electrode is prepared. When Cu+2 concentration is between1.0*10[-5]-1.0*10[-2] mol/L, the ion selective electrode has ultra nernst response, the regression equation is E(Mv)=-56.71 lgCcu (II) -729.91, the correlation coefficient r is 0.9992. The detection lower-limit is 5.0*10[-6] mol/L In Cu[+2] solution at Ph 4.5-5.0, the response time of electrode is less than 30s. The electrode has good stability, high sensitivity and long service life. The electrode is suitable for analytic determination of Cu [+2] in wet metallurgy waste water.
Description
Technical field
The present invention relates to the development of two schiff bases copper (II) ISEs of a kind of salicylidene o-phenylenediamine, can be used for Cu in the hydrometallurgy waste water
2+Assay determination.
Background technology
That ISE has is easy and simple to handle, selectivity is high, the result is accurate, economical and practical, advantage such as just can onlinely use without any need for pre-service and be used widely.Hydrometallurgical copper metallurgy is an important method extracting copper, however the copper that often has some not replace in the method be retained in the water, cause serious pollution to water resource.For the development of copper ion electrodes selective, receive people's attention equally.Developed polytype copper ion electrodes selective at present; The electrode sensitive membrane material that is adopted comprises pyrrolidinyl dithiocarbamate salt, salicylaniline, benzoyl methyl ether, three thiophene derivant classes, sodium type smectite, 2; 9-dimethyl-4; 7-diphenyl-1,10-Phen etc.Each tool relative merits of above-mentioned copper ion electrodes selective, most response time, electrode life and stable aspect not fully up to expectations.
Summary of the invention
The invention reside in and provide that a kind of range of linearity is wide, detection limit is low, highly sensitive, the new copper that electrode life is long, cost of manufacture is low (II) ISE, i.e. two schiff bases copper (II) ISEs of salicylidene o-phenylenediamine.
Conceive as follows: utilize salicylide and o-phenylenediamine to synthesize the two schiff bases (hereinafter to be referred as SPS) of salicylidene o-phenylenediamine; It is mixed with carbon dust as neutral carrier; With the whiteruss is bonding agent; Manufacture copper (II) ISE, optimize condition determination, and be used for the detection of hydrometallurgy and plating wastewater waste water copper with this special response of ability.
Concrete steps are following:
(1) the two schiff bases of salicylidene o-phenylenediamine is synthetic:
Take by weighing 1.16～8.64g o-phenylenediamine in there-necked flask, add 50～200mL absolute ethyl alcohol, reflux to solid dissolves; 3.05～48.8g salicylide in 60～250mL 6.7% (percent by volume) acetate, is slowly joined under the stirring at room in the above-mentioned o-phenylenediamine solution, stir 10min, reflux 4～10h, cooling, suction filtration, drying.And, obtain the two schiff bases of yellow crystal shape target product salicylidene o-phenylenediamine with absolute ethyl alcohol recrystallization 2～3 times.
(2) making of solid paraffin decorating carbon paste electrode:
Get the glass tube of an internal diameter 3.0～6.0mm, polish the two ends of copper rod, clean; Is 1: 2.5～3.5 mixed with solid paraffin and dag by mass ratio, and heat fused is inserted after stirring in the suitable glass tube of internal diameter; Insert the copper rod prepare in advance as lead-in wire from an end; After the cooling, remove the outer unnecessary foreign material of pipe, at smooth paper upthrow sassafras electrode surface; Dig a shallow grooves at electrode surface subsequently; Insert the paraffin carbon paste of the two schiff bases of the obtained salicylidene o-phenylenediamine of doping step (1), then electrode is polished on glossy paper, promptly get the two schiff bases Cu of salicylidene o-phenylenediamine
2+Electrodes selective.
(3) detection method:
The Cu that in the 10mL color comparison tube, adds variable concentrations
2+Standard solution adds the HAc-NaAc buffer solution 1.0mL of 1.5mol/L potassium chloride 1.0mL, pH=5.6 respectively, is diluted with water to scale, changes in the small beaker.Electrode so that the SPS schiff bases after the activation processing is modified is made the work electrode, and saturated calomel electrode is made contrast electrode, measures stable potential response value with acidometer under the stirring condition.
(4) selectivity of electrode:
Adopt mixed solution method, the fixing ion concentration of disturbing changes tested ion concentration, has measured the selectivity factor of part ion, and the result shows that the selectivity factor of this electrode removes Fe
3+Mostly in addition is 10
-2～10
-3, and use NH
4F can eliminate Fe preferably
3+To measuring Cu
2+Interference, explain that a large amount of common ions that exist do not disturb Cu basically
2+Mensuration, promptly electrode has good selectivity.
The present invention has overcome prior art and has had too many shortcomings such as complicacy, and cost of manufacture is low, good stability, highly sensitive, long service life; Electrode is wide for the mensuration range of linearity of copper, detectability is low, can be used to measure the copper in the hydrometallurgy waste liquid.
Description of drawings
Fig. 1 is the two schiff base structure figure of embodiment of the invention salicylidene o-phenylenediamine;
Fig. 2 is the calibration curve of embodiment of the invention copper ion electrodes selective response.
Embodiment
Embodiment:
(1) the two schiff bases of salicylidene o-phenylenediamine is synthetic:
Take by weighing the 5.4g o-phenylenediamine in there-necked flask, add the 60mL absolute ethyl alcohol, reflux to solid dissolves; The 12.2g salicylide in 80mL 6.7% (percent by volume) acetate, is slowly joined under the stirring at room in the above-mentioned o-phenylenediamine solution, stir 10min, reflux 4h, cooling, suction filtration, and with absolute ethyl alcohol recrystallization 2～3 times, drying.Obtain the two schiff bases 13.11g of yellow crystal shape target product salicylidene o-phenylenediamine of accompanying drawing 1, productive rate 64.36%.
(2) making of solid paraffin decorating carbon paste electrode:
Get the glass tube of an internal diameter 3.0～6.0mm, polish the two ends of copper rod, clean; Is 1: 3 mixed with solid paraffin and dag by mass ratio, and heat fused and stirring is rapidly inserted in the suitable glass tube of internal diameter; Insert the copper rod prepare in advance as lead-in wire from an end; After the cooling, remove the outer unnecessary foreign material of pipe, at smooth paper upthrow sassafras electrode surface; Dig out recessed Cao of about 0.5～1.0mm subsequently; Insert the paraffin carbon paste of the two schiff bases of the obtained salicylidene o-phenylenediamine of doping step (1), then electrode is polished on glossy paper, promptly get the paraffin decorating carbon paste electrode.Before the use, with it 1.0 * 10
-3Mol/LCu
2+Standard solution in soak 4h and carry out activation processing, then with washed with de-ionized water to same current potential.
(3) detection method:
At room temperature, measure variable concentrations Cu
2+Potential value in the HAc-NaAc that contains 0.15mol/L KCl (pH=4.2) buffer solution, the drawing curve, its result sees Fig. 2.Cu
2+1.0 * 10
-5～1.0 * 10
-2Appearing in the concentration range of mol/L can this special response, the working curve equation be E (mV)=-56.71lgC
Cu (II)-729.96, correlation coefficient r=0.9992.According to the definition of IUPAC to ISE detectability (LOD), the detection that records electrode is limited to 5.0 * 10
-6Mol/L.
(4) selectivity of electrode:
Adopt mixed solution method, the fixing ion concentration of disturbing changes tested ion concentration, has measured the selectivity factor of part ion, and the result shows that the selectivity factor of this electrode removes Fe
3+Mostly in addition is 10
-2～10
-3, and use NH
4F can eliminate Fe preferably
3+To measuring Cu
2+Interference, explain that a large amount of common ions that exist do not disturb Cu basically
2+Mensuration, promptly electrode has good selectivity.
(5) optimization of electrode sensitive film composition:
Accurately take by weighing the 2.00g carbon dust; The SPS of fusion different proportion processes electrode film and makes an experiment respectively; The consumption of record SPS and the variation relation between the electrode response slope, the result shows: along with the increase of SPS amount, the response slope of electrode increases gradually; When the amount of SPS reached 0.06g, the response slope of electrode reached maximal value; When SPS consumption during greater than 0.06g, downward trend appears in the response slope of electrode.So the optimum amount of SPS is 0.06g, massfraction is 3%.
(6) the pH value is to the influence of electrode response:
In the scope of pH=4.0～5.0, measured C
2+Electrode response potential value in the standard solution.The result shows that pH is at 4.2 o'clock, and the response potential value of electrode promptly reaches maximal value, and keeps constant basically.Experimental selection is determined in the HAc-NaAc buffer solution of pH=4.2 carries out.
(7) response time of electrode and serviceable life:
Among the present invention,, measured electrode pair copper (II) 1.0 * 10 through progressively conversion solution concentration method
-5～1.0 * 10
-2Response characteristic in the mol/L concentration range, the response time that the discovery electrode potential reaches balance and stability is all less than 30s.In 1 week, copper ion electrodes selective behind overactivation to be measured standard solution continuously, the standard deviation that the result finds to measure rate of curve is all less than ± 0.3mV/dec.Same sensitive membrane modified electrode, used for 1 week continuously after, the electrode response slope of a curve occur to descend, and is reduced to below 80% of former potential value.At this moment, can electrode surface polished once more and carries out activation processing, slope can return to initial value again.Explain that electrode has stability and long serviceable life preferably.
(8) application of electrode in analytical test:
Utilize this copper ion electrodes selective to the Cu in the hydrometallurgy waste water
2+Carried out assay determination, institute's test sample article are taken from hydrometallurgy waste water.Mensuration is under the condition identical with the drawing standard curve, to carry out, and with the stable potential response value of being measured, brings the typical curve equation into and obtains its concentration value.Carry out the mark-on recovery test simultaneously, the result sees table 1.It is thus clear that this electrode is used for the analysis of underground wastewater sample, the result is satisfactory.
Table 1 sample analysis result
Claims (1)
1. measure Cu in the waste water for one kind
2+The preparation method of electrodes selective is characterized in that concrete steps are following:
(1) the two schiff bases of salicylidene o-phenylenediamine is synthetic:
Take by weighing 1.16～8.64g o-phenylenediamine in there-necked flask, add 50～200mL absolute ethyl alcohol, reflux to solid dissolves; 3.05～48.8g salicylide in 60～250mL percent by volume is 6.7% acetate, is slowly joined under the stirring at room in the above-mentioned o-phenylenediamine solution, stir 10min, reflux 4～10h, cooling, suction filtration, drying; And, obtain the two schiff bases of yellow crystal shape target product salicylidene o-phenylenediamine with absolute ethyl alcohol recrystallization 2～3 times;
(2) making of solid paraffin decorating carbon paste electrode:
Get the glass tube of an internal diameter 3.0～6.0mm, polish the two ends of copper rod, clean; Is 1: 2.5～3.5 mixed with solid paraffin and dag by mass ratio, and heat fused is inserted after stirring in the suitable glass tube of internal diameter; Insert the copper rod prepare in advance as lead-in wire from an end; After the cooling, remove the outer unnecessary foreign material of pipe, at smooth paper upthrow sassafras electrode surface; Dig a shallow grooves at electrode surface subsequently; Insert the paraffin carbon paste of the two schiff bases of the obtained salicylidene o-phenylenediamine of doping step (1), then electrode is polished on glossy paper, promptly get the two schiff bases Cu of salicylidene o-phenylenediamine
2+Electrodes selective;
(3) detection method:
The Cu that in the 10mL color comparison tube, adds variable concentrations
2+Standard solution adds the HAc-NaAc buffer solution 1.0mL of 1.5mol/L potassium chloride 1.0mL, pH=5.6 respectively, is diluted with water to scale, changes in the small beaker; Electrode so that the two schiff bases of the salicylidene o-phenylenediamine after the activation processing are modified is made the work electrode, and saturated calomel electrode is made contrast electrode, measures stable potential response value with acidometer under the stirring condition.
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| CN102175732B (en) * | 2010-12-08 | 2013-06-19 | 桂林理工大学 | Preparation method of carbon nano tube electrode modified by Schiff base coordination compounds |
| CN102507698A (en) * | 2011-09-23 | 2012-06-20 | 广东省微生物研究所 | Novel sensor for synchronously detecting copper ions and lead ions |
| CN102590310B (en) * | 2012-02-03 | 2014-01-29 | 广州科城环保科技有限公司 | Cuprous ion selective electrode and cuprous ion measuring method thereof |
| CN103674908A (en) * | 2013-07-11 | 2014-03-26 | 四川大学 | Method for detecting bivalent copper ions in water solution and cells by water-soluble 5-sodium sulfonate Salen type Schiff base ligand via fluorescence analysis method |
| CN103940882B (en) * | 2014-04-18 | 2016-04-06 | 上海师范大学 | Trace copper ion sensor and construction method in a kind of water sample |
| CN103926304B (en) * | 2014-05-05 | 2016-01-20 | 盐城工学院 | A kind of photoelectrochemical assay detection method for copper ion |
| CN104961647A (en) * | 2015-06-26 | 2015-10-07 | 西北师范大学 | Fluorescent recognition cupper ion (CU2+) sensor molecules and composition and application thereof |
| CN105806914B (en) * | 2016-03-18 | 2018-01-16 | 河南城建学院 | A kind of copper ion electrodes selective and preparation method thereof |
| MD4523C1 (en) * | 2017-04-07 | 2018-05-31 | Государственный Университет Молд0 | Cu2+ - selective electrode membrane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101178376A (en) * | 2007-09-03 | 2008-05-14 | 江苏工业学院 | Electric potential type chemical sensor and preparation method of full solid-state hydrochloric acid propranolol |
| WO2008145787A1 (en) * | 2007-05-29 | 2008-12-04 | Universitat Rovira I Virgili | Electrodes selective for solid-contact ions based on carbon nanotubes |
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| WO2008145787A1 (en) * | 2007-05-29 | 2008-12-04 | Universitat Rovira I Virgili | Electrodes selective for solid-contact ions based on carbon nanotubes |
| CN101178376A (en) * | 2007-09-03 | 2008-05-14 | 江苏工业学院 | Electric potential type chemical sensor and preparation method of full solid-state hydrochloric acid propranolol |
Non-Patent Citations (1)
| Title |
|---|
| 魏小平，林剑平，李建平.掺杂2，9-二甲基-4，7二苯基-1，10-邻二氮菲的石蜡碳糊铜离子选择性电极的研究.《分析试验室》.2006,第25卷(第7期), * |
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