CN101377473A - Fast quantifying electrolysis method - Google Patents
Fast quantifying electrolysis method Download PDFInfo
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- CN101377473A CN101377473A CNA2007101212252A CN200710121225A CN101377473A CN 101377473 A CN101377473 A CN 101377473A CN A2007101212252 A CNA2007101212252 A CN A2007101212252A CN 200710121225 A CN200710121225 A CN 200710121225A CN 101377473 A CN101377473 A CN 101377473A
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Abstract
The invention discloses a quantitive electrochemical analysis method for fast analyzing substance concentration, which utilizes different electrode systems aiming at different substances. The method determines potential interval between reduction (or oxidization) peaks of the to-be-tested substance by the means of cyclic voltammetry; and based on the interval, the method determines the potential step intervals for three times of potential steps; current-time data is recorded during the three times of potential steps; electric quantity is obtained by integral upon the time with the current peak corresponding to the second potential step interval; the electric quantity is in linear relationship with the concentration of the to-be-detected substance, which can prove the quantitive characteristic. The invention has fast analysis speed and simple operation.
Description
Invention field
The present invention relates to a kind of method of electrochemical quantitative analysis fast, particularly relate to a kind of by quick change current potential and determine the method for measured object concentration with the electron transfer amount in this process.
Background technology
Electrochemical methods is to utilize the electricity of material and the method that electrochemical properties is analyzed.It normally makes sample solution to be analyzed constitute a chemical cell, then according to composition battery some physical quantity and the inner link between its chemistry amount measure, can be divided into amperometry, potentiometry, method of coulometric analysis and volt-ampere analysis etc.At present, the method for electrochemical analysis widespread use is a cyclic voltammetry.This method control electrode electromotive force is with different speed, scan repeatedly with the triangular waveform one or many in time, potential range is to make different and reduction and oxidation reaction can alternately take place on the electrode, and record current-potential curve, can carry out quantitative test by redox peak current on the curve.Use cyclic voltammetry, because the restriction of circulating path and sweep velocity helps little for improving analysis speed.
Method of coulometric analysis is the general name of carrying out the analytical approach of coulometry, also claims coulometry, is a kind ofly to be consumed in the method that the required electric weight of test substance in the solution is measured this content of material quantitatively by mensuration.By coming the method that system is analyzed is called chronocoulometry by the electric charge that flows through in the electrolytic cell circuit in metering a period of time, also claim the timing coulometry, often be used to study the electrode surface adsorption phenomena, and measure electroactive material or surface reactive material electrochemical methods quantitatively in the electrode surface adsorbance.And the selectivity of this method is not good, should not be as the quantitative test in the complicated solution.
Potential step method is to measure corresponding current value with the potential step signal simultaneously as control signal, can draw out electric current-time curve.This method is usually used in the drafting of polarization curve.
Present pollutant analysis method mainly is analysis by titration, gravimetry, ultraviolet/visible/infrared spectrophotometer, gas phase or liquid phase chromatography, gas phase or liquid phase mass spectrometry method, atomic fluorescence/atomic absorption/atomic emission spectrometry etc.These conventional method ubiquity analysis speeds are slow, are difficult to realize shortcomings such as on-line monitoring.And present rapid electrochemical analysis method focuses mostly on aspect biochemical analysis (as Chinese patent CN1975403, CN1325490), and the environmental protection aspect generally is confined to the electrochemical analysis (as Chinese patent CN1645127) of COD in the water and gas sensor aspect (as Chinese patent CN2754096) etc.These method specific aims are stronger, and the versatility deficiency, the material that can detect is more limited.
Summary of the invention
The objective of the invention is in order to solve the slower problem of analytical approach detection speed of existing water pollutant, develop a kind of electrochemical method of high speed detection water pollutant, promptly use the detection selectivity of the continuous step method raising of narrow current potential potential step chronocoulometry, keep the method for express-analysis feature simultaneously.
The principle of rapid electrochemical analysis method provided by the invention is as follows:
Electrolytic tank uses three-electrode system, and its working electrode reply measured object has high selectivity, and contrast electrode is saturated calomel electrode (SCE), and auxiliary electrode is the platinized platinum electrode, and the auxiliary electrode area should be more than or equal to working electrode.
When the current potential that applies on the electrode met or exceeded reduction (or oxidation) current potential of test substance, test substance can obtain (or losing) electronics from electrode, and redox reaction takes place on electrode surface.Because testing concentration difference in the sample, the amount of enrichment is also inequality on electrode surface, therefore when applying certain voltage, the amount of substance difference of electrochemical reaction takes place, and this just causes electron transfer amount difference in the path.By detecting the electric weight that shifts in this process, find that testing concentration is linear dependence in itself and the sample, this is the quantitative basis of this method.
The characteristics of this method are to determine the potential region at reduction (or oxidation) peak of test substance by cyclic voltammetry, this spike potential interval is narrow as far as possible, be called narrow current potential, serve as that foundation is carried out the continuous step test of narrow current potential with this potential region, thereby have only test substance can be reduced (or oxidation).This method that Here it is is got rid of chaff interference, is improved optionally foundation.
Fast quantification electricity analytical method provided by the invention, its step is as follows:
1) battery system in the analytical approach uses three-electrode system, in electrolytic tank, add water sample to be measured, carry out cyclic voltammetry scan in the electrolytic tank of band Luggin capillary, narrow potential step scope (V is determined in reduction (or oxidation) peak position according to test substance on cyclic voltammetry curve
1, V
2).
2) potential control method is improved three potential step methods in the analytical approach, record current-time data (Fig. 1).The potential step scope is 0 → V for the first time
1, current potential arrives V
1The back kept 1～5 second, and in this process, every reduction (oxidation) current potential is higher than (being lower than) V
1Electroactive material can reduce (oxidation) reaction, thereby remove near the chaff interference the electrode; The potential step scope is V for the second time
1→ V
2, current potential arrives V
1The back kept 1～5 second, in this process, and test substance generation electrochemical reduction (or oxidation) reaction, the recorded electronic transfer amount is that electric weight is as quantitative basis; The potential step scope is V for the third time
2→ 0, stablized after the step 1～5 second, make the group of electrode surface revert to original state, be convenient to detect next time.The method T.T. is no more than 15 seconds, and speed is very fast.
3) the sample determination method in the analytical approach is: the normal concentration solution series of preparation test substance, adopt 2) described in method measure respectively and record current-time data.According to electric current-time data, in second time potential step time range, to time integral, obtain charge value with electric current.Charge value-test substance concentration with normal concentration solution series is the straight line that coordinate system adopts least square fitting, is typical curve; According to 2) described method measures the electric current-time data of unknown sample, and calculate charge value and try to achieve unknown sample concentration according to typical curve.
Compared with prior art, advantage of the present invention is:
Compare with gas chromatography/makings logotype method, this method does not need large-scale instrument, and cost is low; Sample need not extract and separate, and pre-treatment is simple; Sample is without chromatographic resolution, and analysis speed is fast.Compare with spectrophotometric method, this method need not developer, and is simple to operate; Compare with atomic absorption/emission spectrometry, this method equipment is simple, and is easy to operate, and range of linearity broad can detect enriched sample.
Description of drawings
Electric current-time data that three potential step methods of Fig. 1 are gathered
Embodiment
Embodiment 1:
Use the nitroreduction enzyme modified electrode to be working electrode, the platinized platinum electrode is an auxiliary electrode, and saturated calomel electrode is a reference, get narrow potential region (0.60V ,-0.80V), begin the negative sense potential step from 0V, snap time is 3 seconds for the first time, and snap time is 3 seconds for the second time, and snap time is 2 seconds for the third time.PH value of solution 7.5 to be measured, reduction peak is quantitative, and solution is without deoxygenation, and the method can be used for detecting water nitrobenzene, the error that the deoxygenation of avoiding ventilating causes, and oxygen reduction has been finished during step more for the first time, can not cause interference.
Embodiment 2:
Use glass-carbon electrode to be working electrode, the platinized platinum electrode is an auxiliary electrode, and saturated calomel electrode is a reference, (0.51V 0.60V), begins the forward potential step from 0V to get narrow potential region, snap time is 2 seconds for the first time, and snap time is 2 seconds for the second time, and snap time is 2 seconds for the third time.PH value of solution 5.6 to be measured, oxidation peak is quantitative, and the method can be used to detect forulic acid concentration.
Embodiment 3:
Use glass-carbon electrode to be working electrode, again-1.0V polarization 1 minute, immerse lead nitrate solution then after 2.0V polarized 2 minutes in advance, activation was used after 10 minutes under stirring condition, platinum electrode is an auxiliary electrode, silver/silver chloride electrode is a reference, get narrow potential region (0.40V ,-0.55V), begin the negative sense potential step from 0V, snap time is 2 seconds for the first time, and snap time is 3 seconds for the second time, and snap time is 2 seconds for the third time.PH value of solution 5.0 to be measured, reduction peak is quantitative, and the method can be used for detecting aqueous solution lead ion (Pb
2+) concentration.
Claims (4)
1, a kind of fast quantification electricity analytical method, its step is as follows:
1) battery system in the analytical approach uses three-electrode system, adds water sample to be measured in the electrolytic tank of band Luggin capillary, carries out cyclic voltammetry scan, and the reduction of the test substance on the cyclic voltammetry curve (or oxidation) peak scope is narrow potential step scope (V
1, V
2);
2) control of Electric potentials adopts three potential step methods in the analytical approach, record current-time data, and the potential step scope is 0 → V for the first time
1, current potential arrives V
1The back keeps a period of time; The potential step scope is V for the second time
1→ V
2, current potential arrives V
1The back keeps a period of time; The potential step scope is V for the third time
2→ 0, keep a period of time after the step;
3) the sample determination method in the analytical approach is: the normal concentration solution series of preparation test substance, employing 2) method is measured respectively and record current-time data described in, according to electric current-time data, in second time potential step time range, with electric current to time integral, obtaining charge value, is the straight line that coordinate system adopts least square fitting with the charge value-test substance concentration of normal concentration solution series, is typical curve; According to 2) described method measures the electric current-time data of unknown sample, and calculate charge value and try to achieve unknown sample concentration according to typical curve.
2, according in the claim 1 1), described three-electrode system is meant the system that is made up of working electrode, contrast electrode, auxiliary electrode; The sweep velocity of described cyclic voltammetry scan is 10～500mV/s; Described oxidation/reduction peak potential region refers to that oxidation/reduction peak has just occured to the potential region of end, and its scope is at 0.01～0.30V.
3, according in the claim 1 2), described three potential step methods are meant the method for the continuous step of CONTROLLED POTENTIAL three times, each step begins to finish the used time less than 0.5 second to potential change from potential change, and three potential change time adds the retention time and is no more than 15 seconds; Described a period of time is meant 1～5 second.
4, according in the claim 1 3), the normal concentration solution series of described test substance is meant the concentration known standard model of 2～20 variable concentrations, its pH should be identical with the actual analysis sample; Described second time the potential step time range be meant since the second time step to a period of time step begins for the third time; Described typical curve, its linearly dependent coefficient needs greater than 0.9.
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| CN2007101212252A CN101377473B (en) | 2007-08-31 | 2007-08-31 | Fast quantitative electroanalysis method |
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| CN2007101212252A CN101377473B (en) | 2007-08-31 | 2007-08-31 | Fast quantitative electroanalysis method |
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| CN101377473B CN101377473B (en) | 2012-04-25 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101782545A (en) * | 2010-03-09 | 2010-07-21 | 中国科学院过程工程研究所 | Method for purifying ionic liquid concentration |
| CN104062339A (en) * | 2014-07-09 | 2014-09-24 | 华南师范大学 | [Ru(tatp)3]<2+> modified electrode and method for detecting glucose, uric acid and ascorbic acid in blood by adopting electrode |
| CN110186981A (en) * | 2019-04-19 | 2019-08-30 | 九江德福科技股份有限公司 | A kind of Quantitative Monitoring method of chloride ion |
| CN113219025A (en) * | 2021-05-07 | 2021-08-06 | 安徽大学 | Method for quantitatively detecting potassium bromate |
| CN113418824A (en) * | 2021-05-07 | 2021-09-21 | 华东理工大学 | Method for testing gas adsorption capacity |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4404130A1 (en) * | 1994-02-09 | 1995-08-10 | Siemens Ag | Electrochemical determination of the oxygen concentration |
| AUPN661995A0 (en) * | 1995-11-16 | 1995-12-07 | Memtec America Corporation | Electrochemical cell 2 |
| EP1055926A3 (en) * | 1999-05-28 | 2001-11-14 | Kabushiki Kaisha Meidensha | Electrochemical assay using an electroconductive diamond-coated electrode, and electrochemical assay system based thereon |
| CN1715899A (en) * | 2004-07-02 | 2006-01-04 | 中国科学院福建物质结构研究所 | A kind of preparation method of novel residual chlorine detecting electrode |
-
2007
- 2007-08-31 CN CN2007101212252A patent/CN101377473B/en active Active
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101782545A (en) * | 2010-03-09 | 2010-07-21 | 中国科学院过程工程研究所 | Method for purifying ionic liquid concentration |
| CN104062339A (en) * | 2014-07-09 | 2014-09-24 | 华南师范大学 | [Ru(tatp)3]<2+> modified electrode and method for detecting glucose, uric acid and ascorbic acid in blood by adopting electrode |
| CN104062339B (en) * | 2014-07-09 | 2016-08-31 | 华南师范大学 | [Ru (tatp) 3] 2+ modified electrode and the method being used for detecting glucose in blood, uric acid and ascorbic acid thereof |
| CN110186981A (en) * | 2019-04-19 | 2019-08-30 | 九江德福科技股份有限公司 | A kind of Quantitative Monitoring method of chloride ion |
| CN113219025A (en) * | 2021-05-07 | 2021-08-06 | 安徽大学 | Method for quantitatively detecting potassium bromate |
| CN113418824A (en) * | 2021-05-07 | 2021-09-21 | 华东理工大学 | Method for testing gas adsorption capacity |
| CN113418824B (en) * | 2021-05-07 | 2023-02-10 | 华东理工大学 | Method for testing gas adsorption capacity |
| CN113219025B (en) * | 2021-05-07 | 2023-07-25 | 安徽大学 | Method for quantitatively detecting potassium bromate |
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