CN102746222A - Quinolylazo complexing reagent, preparation method thereof, and application thereof - Google Patents
Quinolylazo complexing reagent, preparation method thereof, and application thereof Download PDFInfo
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- CN102746222A CN102746222A CN2012101623918A CN201210162391A CN102746222A CN 102746222 A CN102746222 A CN 102746222A CN 2012101623918 A CN2012101623918 A CN 2012101623918A CN 201210162391 A CN201210162391 A CN 201210162391A CN 102746222 A CN102746222 A CN 102746222A
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Abstract
The invention belongs to the field of analytical chemistry, and specifically relates to a quinolylazo photometric analysis complexing reagent used in silver determination. The invention also relates to a preparation method of the analysis reagent, and an application of the reagent in determinations of silver contents in actual samples. The complexing reagent is named as 2-(2-quinolylazo)-4,5-dimethoxyaniline, and has a chemical structure represented by the general formula. With silver, the reagent can form a stable red complex, which has a light absorbance proportional to the silver content. Therefore, the reagent can be used in silver content determination, and has good selectivity and sensitivity to silver.
Description
Technical field
The invention belongs to the analytical chemistry field, more particularly, the present invention relates to a kind of quinoline azo class photometric analysis reagent that silver is measured that is used for.Simultaneously, the invention still further relates to the preparation method of said analytical reagent and be used for the mensuration of actual sample silver content.
Technical background
Silver is a kind of important environmental element, and silver or silver salt can be calm at skin, eyes and mucous membrane after getting into human body, produce pathology.Thereby the mensuration of silver is significant in the environmental sample, and the mensuration of silver has been classified one of index of environment conventional sense as.The measuring method of silver mainly contains spectrophotometry, atomic absorption spectrometry, inductively coupled plasma emission spectrography, inductively coupled plasma mass spectrometry, electrochemical process etc. at present.Because plant and instrument is simple, easy and simple to handle, analysis cost is low, beam split range method remains the most frequently used method.Because spectrophotometric analysis depends primarily on the performance of photometric analysis reagent; Seeking analytical reagent highly sensitive, that selectivity is good is the focus of photometric analysis research; Only continually develop out new analytical reagent highly sensitive, that selectivity is good, just the performance of photometric analysis constantly is improved, range of application constantly is expanded.
Summary of the invention
The objective of the invention is to deficiency to prior art; A kind of new new analytical reagent of quinoline azo class is provided, and this reagent can generate stable red complex with silver, and its absorbancy and silver content are directly proportional; The mensuration that can be used for silver content has good selectivity and sensitivity to silver.
Another object of the present invention provides a kind of preparation method of said reagent.
Further aim of the present invention provides said reagent in the Trace Silver Application in Photometric Analysis.
The object of the invention is achieved through following technical proposals.
Except as otherwise noted, the percentage ratio that is adopted among the present invention is mass percent.
A. the present invention has carried a kind of new quinoline azo class complexometric reagent, and it has following structural formula:
Its called after 2-(2-quinoline azo)-4, the 5-dimethoxyaniline.
B. the invention provides a kind of preparation method of said reagent, this method adopts the step of following order:
(1) diazotization---the 2-quinolylamine of 0.05 mol is dissolved in the 350 ml absolute ethyl alcohols, adds 2.0 g sodium amides, heating in water bath 4 h that reflux.Add 15 g Isopentyl nitrites then, refluxed 30 minutes again, cooling can obtain diazonium salt.
(2) coupling---in diazonium salt solution, add 3,4-dimethoxyaniline 0.02 mol, and under logical carbon dioxide conditions, stir 0.5 h, and placement is spent the night, and the most ethanol of pressure reducing and steaming leaches deposition and can get bullion.
(3) bullion is purified---and bullion is with 25～35% ethyl alcohol recrystallization 2～3 times; Recrystallization is operating as: add 25～35% ethanol 45 mL in every gram bullion, heating lets it dissolve fully, slowly cools to room temperature (having red needle-like crystal to separate out); Put into refrigerator again and continue to be cooled to (crystal of separating out further increases) below 4 ℃; Suction filtration is isolated deposition and vacuum-drying, promptly makes required complexometric reagent, and ultimate yield is 42%.
C. the physical and chemical parameter of reagent and structure are identified:
Test-run a machine of the present invention is the scarlet powder, is soluble in methyl alcohol, acetone, ethanol isopolarity organic solvent, is slightly soluble in water.Ir spectra (the cm of reagent
-1); 3336,3420 λ-NH
21058 λ-C-O-; 1625,1567,1580,1,450 1386, λ-C=C-, λ-C=N-, λ-N=N-; 859,764,3087, λ-Ar-H, σ-Ar-H; 1325 λ-C-N-; 1395,2925 λ-CH
3Ultimate analysis: theoretical value (calculated value) %, C 66.22 (66.11), and H 5.23 (5.38), and N 118.17 (18.06); Proton nmr spectra (solvent: CD
3OD) (σ ppm): 3.82 (s, 3H ,-OCH
3); 3.88 (s, 3H ,-OCH
3), 6.82 (s, 1H, Ar-H), 6.97 (s, 1H, Ar-H); (7.32 m, 1H, quinoline ring); (7.55 m, 1H, quinoline ring); (7.64 d, 1H, quinoline ring); (7.81 d, 1H, quinoline ring); (8.06 d, 1H, quinoline ring); (8.15 d, 1H, quinoline ring), in conjunction with synthetic route, provable product is a title product.
D. the present invention is based on new synthetic reagent, solid phase extraction concentration is provided, the novel method of spectrophotometry silver, and this method is applied in the analytical test of actual sample, its specific practice is following:
(1) sample preparation---in sample, be the sample of ionic state for silver, can directly measure, for the sample that silver exists with combined, measure behind the Specimen eliminating again, digestion procedure is seen the practical implementation case.
(2) solid phase extraction concentration---get an amount of sample solution or standard specimen (total argentiferous < 4.0 μ g) and in 100 mL Erlenmeyer flasks, add the EDTA solution of 5 mL 5%, add 2 ml, 1% emulsifying agent-OP solution then; 5 ml pH are borax-sodium hydroxide buffer solution of 11.0; 5.0 ml 0.05% developer (reagent of the present invention), constant volume shakes up to 100 mL; Place 10 min; Colour developing liquid with the flow velocity of 10 ml/>min through the anti-phase solid phase extraction column, has crossed the back with the flow velocity of 10 ml/min with 2.0 ml ethanol (include 0.01 mol/L pH be 11.0 Pyrrolidine-acetate buffer salt) eluant solution, elutriant confession analysis usefulness.
(3) spectrophotometric analysis condition determination---elutriant is reference with the reagent blank, and using volume is the 1 cm semimicro cuvette of 0.5 mL, measures absorbancy in 526 nm places, with the accurate solution of the silver label curve of working, measures content silver-colored in the actual sample.
The principle of work of analytical procedure provided by the invention:
Reagent according to the invention can optionally reaction generates stable hydrophobicity colored complex with silver in weak alkaline medium; This complex compound can quantitatively be adsorbed by the anti-phase solid-phase extraction column; Using ethanol instead is that eluent can quantitatively wash the complex compound of anti-phase SPE on-column enrichment, thereby reaches the solid phase extraction concentration to silver; The content and the absorbancy of silver are directly proportional in the solution after the enrichment, can realize the quantitative analysis of silver content.
---detailed experimental conditions
(1) absorbing wavelength: colour developing complex compound maximum absorption wavelength is 500 nm in the elutriant medium, and the reagent blank maximum absorption is 360 nm, and contrast gradient Δ λ is 140 nm, and the system contrast gradient is bigger.
(2) influence of color acidity: system develops the color in weak alkaline medium; At pH is that 10.0～12.9 scope internal absorbances are maximum and stable; It is borax-sodium hydroxide buffer solution controlling acidity of 11.0 that pH is selected in experiment for use; Consumption can be controlled at stable range to pH about 5 ml, experiment is selected for use and added 5 ml.
(3) surfactant selection and consumption: developer of the present invention and complex compound thereof are poorly soluble in the aqueous solution; Need with the surface active agent solubilization system just stable; Tested of the influence of some common tensio-active agents to system; Experiment shows: cationic surfactant, aniorfic surfactant and non-ionics all have good solublization to system; But cationic surfactant and aniorfic surfactant do not have sensitization to system, on the contrary can reducing sensitivity.Non-ionics has certain sensitization to system, and its effect of enhanced sensitivity is: emulsifying agent-OP＞tween-80＞tween 20＞Tween-60.1.0% emulsifying agent-OP consumption is all stable at 1～5 ml internal absorbance, and 2 ml are selected in experiment for use.
(4) selection of developer consumption: experiment shows: 0.05% developer consumption is maximum and stable at 4～8 ml internal absorbances, and 5 ml are selected in experiment for use.
(5) stability of colour temp and system: system is colour developing rapidly at room temperature, place 5 min after absorbancy can reach stable, colour developing fully back system can be stablized 5 h at least.
(6) SPE condition: because the pH scope that common bonded silica gel anti-phase solid-phase extraction column uses is 2-8; And the pH of colour developing colour developing medium is 11 in this experiment; Can not use common reversed-phase bonded silica SPE column solid phase extraction, therefore the Waters Xterra of particular fillers is selected in experiment for use
TMRP
18Solid phase extraction column, this pillar all have good stability in pH is 1～12 scope.
Waters Xterra
TMRP
18Solid phase extraction column is a reversed-phase column; Pillar is to the available hydrophobic association principle explanation of the extraction of the complex compound of mineral ion and reagent generation, 3,5-DB-PDAB and 3; 5-DB-PDAB has certain hydrophobicity with the complex compound that silver generates; Can be enriched on the post during with the aqueous solution, use the big solvent of little solvent intensity (ethanol, acetonitrile, THF etc.) wash-out instead and just can wash complex compound, thereby reach example enrichment through pillar.Sample (colour developing liquid) with 10 ml/min flow velocitys through the good pillar of activation; Through the effluent behind the pillar is colourless, and measuring after the collection effluent concentrates does not have silver to detect again, and explains that the micella complex compound of generation and excessive reagent all can be retained on the pillar fully; Selecting capacity for use is the pillar of 30 mg; Silver content can not surpass the loading capacity of pillar during less than 100 μ g, and the maximum of silver is merely 2.0 μ g in this experiment, so leakage can not take place.Micella complex compound and reagent have been tested with enrichment on the different eluent wash-out pillars; With THF, methyl alcohol, acetone and ethanol etc. micella complex compound and reagent are washed fully; Because ethanol low price; Volatility is weak and nontoxic, and historical facts or anecdotes is tested and selected ethanol for use, in ethanol, contains 0.01 mol/L pH and is Pyrrolidine-acetate buffer eluting salt better effects if of 11.0 and can keep in the elution process complex compound stable.Therefore experiment selects for use ethanol (include 0.01 mol/L pH be 11.0 Pyrrolidine-acetate buffer salt) to be eluent; Experiment shows that the ethanol about flow velocity with 10 ml/min is with 2.0 ml can wash the micella complex compound and the reagent of enrichment on the pillar fully; Ethanol mutually in; The abosrption spectrogram of complex compound does not change, explain the colour developing product come together into ethanol mutually in the back structure do not change.
(7) working curve: under selected experiment condition; Silver content meets Beer's law in 0.01～1.0 μ g/ml; Equation of linear regression is A=0.0467+1.593 C (μ g/ml), and r=0.9994 can calculate molar absorptivity ε=1.82 * 10 from regression equation
5L.mol
-1.cm
-1
(8) influence of coexisting ion: for the Ag of 1.0 μ g
+, relative error is ± 5%, following amount ion does not disturb (mg): NO
3 -, BrO
3 -, ClO
4 -, K
+, Na
+, Ca
2+, NH
4 +(20); IO
3 -, PO
4 3-, Mg
2+, Al
3+, B (III), SO
4 2-, V (V) (5), Mo (VI), Zn
2+, Ce (IV), SiO
3 2-(2); Cr
3+, Ti (IV), Mn
2+, Th (IV), S
2O
3 2-, Fe
3+(1); Cl
-, Sn (IV), Pd
2+, Ru (III), W (VI) (0.5); Pb
2+, Ir (IV), Rh (III), As (V), Au (III), Pt (II), Br
-, Tl
3+(0.01); Co
2+, Ni
2+, Cu
2+, Hg
2+, SCN
-(0.2); Cd
2+, CN
-, I
-(0.005); Common ion does not all disturb, and system has selectivity preferably.
(9) mensuration formed of complex compound: can record in the complex compound 3 by mole ratio method and continuous variation method, 5-DB-PDAB and Ag
+Mol ratio 2:1.
Compared with prior art, the present invention has following outstanding advantage:
New analytical reagent provided by the invention: 2-(2-quinoline azo)-4, the 5-dimethoxyaniline can generate stable complex compound with silver in weak medium.This complex compound can be used the anti-phase solid phase extraction concentration; The complex compound of enrichment is the quantitative silver of wash-out enrichment of eluent, the silver-colored available aas determination in the elutriant with ethanol (including 1% acetic acid).Compare with ordinary method; The complex compound that this method agents useful for same and silver generate is highly stable, and silver is had good selectivity, and silver complex can be by quantitative enrichment and wash-out; The method recovery is very high; The enrichment multiple can surpass 200 times, because the high enrichment multiple of SPE has remedied the lower shortcoming of spectrophotometry sensitivity, the very simple light-intensity method of plant and instrument also can be applied in the ultra-trace silver mensuration.
Embodiment
Through specific embodiment given below and typically used embodiment, can further be well understood to the present invention.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification protection scope of the present invention.
Embodiment 1
---the mensuration of silver in the environmental water sample
Accurately take by weighing water sample an amount of (silver content is less than 30 μ g) in small beaker, add the 1 mL vitriol oil, 4 mL concentrated nitric acids and 2 mL, 30% hydrogen peroxide; On hot plate, be heated to and emit white cigarette; Add 1 mL perchloric acid heating evaporation again and do, add 10 ml, 2% nitric acid dissolve residue, change in the 100 ml Erlenmeyer flasks near;, transfer pH near approximately neutral; Add the EDTA solution of 5 mL 5% in this solution, add 2 ml, 1% emulsifying agent-OP solution then, 5 ml pH are borax-sodium hydroxide buffer solution of 11.0; 5.0 ml 0.05% developer (reagent of the present invention), constant volume shakes up to 100 mL; Place 10 min; Colour developing liquid, has been crossed afterwards with the flow velocity of 10 ml/min with 2.0 ml ethanol (include 0.01 mol/L pH be 11.0 Pyrrolidine-acetate buffer salt) eluant solution through the anti-phase pillar with the flow velocity of 10 ml/min, and elutriant is reference with the reagent blank; Using volume is the 1 cm semimicro cuvette of 0.5 mL; Measure absorbancy in 526 nm places,, measure the content of silver in the actual sample with the accurate solution of the silver label curve of working.Measure the result and compare with atomic absorption (AAS) method, the result is consistent.
Embodiment 2
---the mensuration of silver in the pedotheque
Take by weighing pedotheque 0.5 g in tetrafluoroethylene microwave digestion bottle, add 2.0 mL concentrated nitric acids and 3 mL hydrofluoric acid, in the microwave digestion stove, clear up 25 min with the power of 800 W; Cleared up back heating evaporation on hot plate and done,, regulated the pH value to neutrality with the nitric acid dissolve residue of 20 mL 5% near; Add the EDTA solution of 5 mL 5% in this solution, add 2 ml, 1% emulsifying agent-OP solution then, 5 ml pH are borax-sodium hydroxide buffer solution of 11.0; 5.0 ml 0.05% developer (reagent of the present invention), constant volume shakes up to 100 mL; Place 10 min, colour developing liquid, has been crossed afterwards with the flow velocity of 10 ml/min with 2.0 ml ethanol (include 0.01 mol/L pH be 11.0 Pyrrolidine-acetate buffer salt) eluant solution through the anti-phase pillar with the flow velocity of 10 ml/min; Elutriant is reference with the reagent blank, and using volume is the 1 cm semimicro cuvette of 0.5 mL, measures absorbancy in 526 nm places; With the accurate solution of the silver label curve of working, measure the content of silver in the actual sample.Measure the result and compare with atomic absorption (AAS) method, the result is consistent.
Claims (4)
1. quinoline azo class complexometric reagent is characterized in that having formula:
This reagent called after 2-(2-quinoline azo)-4, the 5-dimethoxyaniline.
2. the preparation method of the described quinoline azo of claim 1 a class complexometric reagent is characterized in that adopting following steps:
The 2-quinolylamine of (1) 0.05 mol is dissolved in the 350 ml absolute ethyl alcohols, adds 2.0 g sodium amides, heating in water bath 4 h that reflux; Add 15 g Isopentyl nitrites then, refluxed 30 minutes again, cooling makes diazonium salt;
(2) in diazonium salt solution, add 3,4-dimethoxyaniline 0.02mol stirs 0.5 h under the condition of logical carbonic acid gas, and placement is spent the night, and the most ethanol of pressure reducing and steaming leaches deposition and makes bullion;
(3) bullion promptly obtains required analytical reagent with 25～35% ethyl alcohol recrystallization 2～3 times.
3. the preparation method of quinoline azo class complexometric reagent as claimed in claim 1; The recrystallization that it is characterized in that bullion is operating as: add 25～35% ethanol 45 mL in every gram bullion; Heating lets it dissolve fully, is cooled to room temperature gradually to there being red needle-like crystal to separate out, and puts into refrigerator again and continues to be cooled to below 4 ℃; Suction filtration is isolated deposition and vacuum-drying, makes required complexometric reagent.
4. reagent as claimed in claim 1 is used for the developer of formation determination sample silver content.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101623918A CN102746222A (en) | 2012-05-23 | 2012-05-23 | Quinolylazo complexing reagent, preparation method thereof, and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101623918A CN102746222A (en) | 2012-05-23 | 2012-05-23 | Quinolylazo complexing reagent, preparation method thereof, and application thereof |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012101623918A Pending CN102746222A (en) | 2012-05-23 | 2012-05-23 | Quinolylazo complexing reagent, preparation method thereof, and application thereof |
Country Status (1)
| Country | Link |
|---|---|
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3859303A (en) * | 1971-08-09 | 1975-01-07 | Fuji Photo Film Co Ltd | Spiro(indoline-2,5'-pyrazoline)derivatives |
| US4327173A (en) * | 1980-01-23 | 1982-04-27 | Fuji Photo Film Co., Ltd. | Color photographic light-sensitive material |
-
2012
- 2012-05-23 CN CN2012101623918A patent/CN102746222A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3859303A (en) * | 1971-08-09 | 1975-01-07 | Fuji Photo Film Co Ltd | Spiro(indoline-2,5'-pyrazoline)derivatives |
| US4327173A (en) * | 1980-01-23 | 1982-04-27 | Fuji Photo Film Co., Ltd. | Color photographic light-sensitive material |
Non-Patent Citations (2)
| Title |
|---|
| QIUFEN HU，等: "Solid Phase Extraction and Spectrophotometric Determination of Silver with 2-(2-Quinolylazo)-5-diethylaminoaniline as Chromogenic Reagent", 《MICROCHIMICA ACTA》 * |
| 胡秋芬: "固相萃取在几种环境元素分析中的研究应用", 《云南大学硕士学位论文》 * |
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Application publication date: 20121024 |