CN1122002A - Polarographic anode dissolving-out analysis method - Google Patents
Polarographic anode dissolving-out analysis method Download PDFInfo
- Publication number
- CN1122002A CN1122002A CN 94110779 CN94110779A CN1122002A CN 1122002 A CN1122002 A CN 1122002A CN 94110779 CN94110779 CN 94110779 CN 94110779 A CN94110779 A CN 94110779A CN 1122002 A CN1122002 A CN 1122002A
- Authority
- CN
- China
- Prior art keywords
- enrichment
- time
- computing machine
- curve
- period
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Abstract
The anodic stripping voltammetry for polarographic analysis, an improvement on the patent CN93207233.X, has two measure periods, each including cleaning, enrichment, standing and scanning. One enrichment phase is longer than another. By substraction between variation curves of working electrode currents with scan voltage for two enrichment phases, a new curve is obtained for analytic calculation, which has higher peak, benefiting measurement.
Description
The present invention relates to a kind of polarographic method, particularly relate to a kind of anodic stripping voltammetry.
Anodic stripping voltammetry is to measure a kind of important method that underwater gold belongs to ion concentration.The principle of this method is, at first the metallic ion in the water carried out electrolytic reduction under constant potential, by the metal enrichment of electrolytic reduction on working electrode.Then, apply reverse scan voltage on electrode, even working electrode changes the current potential of test solution is linear from low to high in some way, making the burning that is reduced on working electrode is the metallic ion stripping, and the generation oxidation current, the record oxidation current is with the change curve of scanning voltage.To specific metal, when potential change arrives its oxidizing potential, become metallic ion with regard to oxidized (" stripping "), peak current appears this moment, the peak height of peak current is directly proportional with the concentration of metallic ion, can calculate the concentration of institute's metal ion in the water by the peak height of measuring peak current.To measure by polarograph during actual measurement, generally will pass through " cleaning ", " enrichment ", " leaving standstill ", " scanning " four steps." cleaning " is to add final voltage between electrode, stirs by stirrer, makes residually on the working electrode to treat the measured ion stripping, to reduce the influence of test next time; " enrichment " is to add starting potential between electrode, and stirs with stirrer, makes metallic ion to be measured electrolytic reduction on working electrode; " leaving standstill " is to stop to stir, and reduces the disturbance of solution, to reduce the signal noise that is produced by disturbance; " scanning " is that interelectrode voltage changes to final voltage with certain speed from starting potential, makes the burning stripping of reduction on working electrode, and the writing task electrode current is with the change curve of scanning voltage, so that carry out qualitative, quantitative test simultaneously.Adopt the actual working electrode current signal that measures of this method to be made up of two parts superposition, first is by the oxidation stripping current signal of the metal of enrichment, and second portion is the background current signal of solution.The background current signal mainly is by the H in the solution
+, O
2And the H on the electrode
gCan not be produced by the material of enrichment with many in some sample.The big I of first's current signal changes along with the length of enrichment time, and the length of second portion current signal and enrichment time is irrelevant basically.The relation of background current and scanning voltage is actually a curve, is also referred to as baseline.Be in the stripping current signal generation distortion of obvious inclination of baseline or sweep, the stripping peak is difficult to prepare to measure or be beyond recognition at all, therefore makes the raising of sensitivity and the reduction of detection lower limit be subjected to great limitation.On June 1st, 1994, announced one on the utility model patent communique and be called the patent of " polarograph compensator ", application number: 93207233.X, Granted publication number: CN2167368Y.Disclose a kind of polarograph that zero compensation device, gradient compensation device and curve compensator are installed in the instructions of this patent,, made through the measuring-signal baseline of over-compensation comparatively straight within the specific limits by curve compensation.This compensator can only compensate H
+And H
gInfluence, it provides one and H
+And H
gThe compensated curve that the measuring-signal baseline shape that is influenced is close, phase place is opposite.But the background current signal is very complicated in the actual measurement, can not full remuneration H with this compensator
+And H
gInfluence, to O
2Wait the influence of other material to compensate.Thereby the higher sensitivity of the very difficult use of practical application, especially difficult when several metal ion species are measured simultaneously.In addition, when adopting the polarograph that has this compensator to carry out actual measurement, must manage to make compensated curve and be alignd, troublesome poeration, waste Measuring Time by the measuring-signal baseline of compensated part.
The objective of the invention is to design a kind of Polarographic anode dissolving-out analysis method, it can obtain a new curve from the influence of working electrode electric current with background correction electric current the change curve of scanning voltage, and the stripping peak of test substance is obvious in this curve.
The object of the present invention is achieved like this, a kind of Polarographic anode dissolving-out analysis method, and it is divided into two test periods.Each parcel cleaning, enrichment, leave standstill, scan four steps, its special character is test period:
(1) enrichment time of one of them test period is shorter, makes metallic ion to be measured electrolysis enrichment on working electrode less.The working electrode electric current that obtains after the scanning deposits among the RAM of computing machine with the change curve of scanning voltage;
(2) enrichment time of another test period is longer, makes metallic ion to be measured electrolysis enrichment on working electrode more.Scan with the scanning voltage identical than short test period with enrichment time, the working electrode electric current that obtains after the scanning deposits among the RAM of computing machine with the change curve of scanning voltage;
(3) with computing machine the working electrode electric current that obtains in test period in longer enrichment time is differed from the change curve of scanning voltage with the change curve of scanning voltage and the working electrode electric current that obtains in test period in shorter enrichment time and subtract computing, the curve that obtains after difference subtracts deposits among the RAM of computing machine;
(4) the curve output that obtains after with the output device of computing machine difference being subtracted is carried out analytical calculation to the curve of output.
Two test periods of the present invention adopt same working electrode to carry out in same electrolytic cell.Lack in the test period of (polarograph that has can be made as 0 with enrichment time) in enrichment time, metallic ion to be measured electrolysis enrichment on working electrode is less, and the peak height at its stripping peak is lower.In long test period, metallic ion to be measured electrolysis enrichment on working electrode is more in enrichment time, and the peak height at its stripping peak is higher.The working electrode electric current that will obtain in test period in long enrichment time differs from the change curve of scanning voltage with the change curve of scanning voltage and the working electrode electric current that obtains in test period in short enrichment time and subtracts, and obtains the change curve of a new electric current with scanning voltage.The selection of enrichment time length should be selected according to different test condition, and long enrichment time should make that working electrode is unsaturated to exceed, and short enrichment time generally should be less than 1/5th of long enrichment time.
The present invention can adopt following more detailed step to carry out by computing machine:
(1) in the RAM of computing machine, opens up figure storage portions MM1, MM2, MM;
(2) in the RAM of computing machine, open up storage portions, be respectively:
QM1: be used to deposit scavenging period QT1,
QM2: be used to deposit scavenging period QT2,
FM1: be used to deposit enrichment time FT1,
FM2: be used to deposit enrichment time FT2,
JM: be used to deposit time of repose JT,
SM: be used to deposit ST or sampling period T sweep time;
(3) in the RAM of computing machine, open up a field and make " parity indicator ", be used to deposit the i value, i=1 when initial;
(4) by input equipment QT1, QT2, FT1, FT2, JT, ST or T are set and deposit in respectively among storage portions QM1, QM2, FM1, FM2, JM, the SM, wherein FT1 is longer than FT2;
(5) according to sweep time ST value and sampled point number N calculate the sampling period
Or the sampling period T of computing machine is imported in employing in advance;
(6) start computing machine,, be designated as " 1 " under decision QT1, QT2, FT1, FT2, MM1 and MM2 are selected and still be " 2 " according to the currency of i;
(7) the I/O mouth by computing machine sends " cleaning " commencing signal, starts " timer " among the CPU simultaneously, and the stand-by period is QTi;
(8) arrive when the QTi time, the I/O mouth sends termination " cleaning " signal and " enrichment " commencing signal, restarts " timer " among the CPU simultaneously, and the stand-by period is FTi;
(9) arrive when the FTi time, the I/O mouth sends termination " enrichment " signal and " leaving standstill " commencing signal, restarts " timer " among the CPU simultaneously, and the stand-by period is JT;
(10) arrive when the JT time, the I/O mouth sends termination and " leaves standstill " signal and " scanning " commencing signal, starts " counter " among the CPU simultaneously, and counting adds up to N (sampling is always counted);
(11) start " timer " among the CPU simultaneously, the stand-by period is T, when the T time then, close by " timer ", the working electrode signal of input is deposited among the figure storage portions MMi, counter subtracts 1;
(12) if Counter Value is not equal to 0, repeating step (11) if Counter Value equals 0, has drawn the working electrode electric current this moment and has deposited figure storage portions MMi in the change curve MAPi of scanning voltage;
(13) change i value, even original i=1, i=2 then, if i=2 originally, i=1 then, repeating step (6) be to (12), at this moment, goes out the work electrode current again and deposit among the figure storage portions MMi with the change curve MAPi of scanning voltage;
(14) by the keyboard appointment curve M AP1 and MAP2 are subtracted each other, result curve deposits among the MM, by output device result curve is exported, and the curve of exporting is carried out analytical calculation.
In the above-mentioned steps, if begin to be provided with sampling period T, then needn't input scan time ST, be exactly total sampling period sweep time T takes advantage of the sampling points N.If begin to be provided with ST sweep time, then needn't the input sample period T, the sampling period can adopt
Calculate.QT1 of the present invention, QT2, FT1, FT2, JT, ST or T can be by the keyboard settings, wherein ST also can be by the waver setting, ST value sweep time that each of waver grade correspondence one is concrete, what shelves computing machine is in by differentiating waver, its corresponding ST value is stored among the storage portions SM, after starting potential and final voltage were determined, " scanning " time can determine " scanning " speed; Working electrode voltage in " cleaning ", " enrichment ", " leaving standstill ", " scanning " process can directly be cheated out by computing machine, also can be provided by the mimic channel that computing machine sends control signal control polarograph; FT2 generally should be less than 1/5th of FT1.
The present invention deposits the oxidation stripping current curve of the element to be measured in two test periods and the superposition curve of background current curve (being the change curve of working electrode electric current with scanning voltage) in by sampling with computing machine in the data memory (RAM) of computing machine and keeps, because enrichment time length difference in two test periods, the therefore peak height difference of the oxidation stripping electric current of the element to be measured that in this two test periods, obtains.Being used in working electrode electric current that long enrichment time obtains in test period subtracts each other with the change curve of the working electrode electric current that obtains in test period in short enrichment time with scanning voltage with the change curve of scanning voltage, obtain the change curve of a new electric current with scanning voltage, peak height in this curve is high poor with at the peak height of the oxidation stripping electric current of the to be measured element of short enrichment time in test period of the honeybee of the oxidation stripping electric current of the to be measured element of long enrichment time in test period, the peak height in this curve and the concentration of element to be measured have the better linearity relation, can carry out quantitative test by " standard addition method ".Deducted the background current curve in the new curve that obtains after difference subtracts, to H
+, H
g, O
2And the influence that other material causes can both compensate, and need not carry out the deoxygenation operation in the measuring process, the baseline straightening of spectrogram, the stripping current peak obviously can be debated, be convenient to analytical calculation, improved the sensitivity of measuring, reduced measurement lower limit concentration of element to be measured.Particularly in measuring water during the concentration of multiple metallic ion, help can saving the time of measurement like this with method of the present invention to the gathering and measurings simultaneously of several metal ion species in the same water sample, make the measuring process simplification.Adopt the present invention to measure, " cleaning " time, " enrichment " time and " scanning " time can be set easily according to different testing conditions, article two, to subtract process be with the working electrode current subtraction under the same scan voltage in two curves by computing machine to the difference of curve, do not need the artificial alignment of adjusting, the new curve that obtains after subtracting each other deposits in the data memory of computing machine and keeps, be convenient to output and carry out analytical calculation, whole measuring process realizes full automation, has improved analysis speed.
Below in conjunction with accompanying drawing embodiment of the present utility model is described in detail.
Fig. 1 is the circuit block diagram of the used instrument and equipment of the present invention.
Fig. 2 is realization computer program process flow diagram of the present invention, and as Figure of abstract.
Fig. 3 is the working electrode electric current that obtains in test period in the long enrichment time change curve with scanning voltage.
Fig. 4 is the working electrode electric current that obtains in test period in the short enrichment time change curve with scanning voltage.
The electric current that Fig. 5 obtains after subtracting each other for Fig. 3 and Fig. 4 is with the change curve of scanning voltage.
The present invention can adopt instrument and equipment as shown in Figure 1 to realize that computing machine adopts S098CPU, and its external unit has keyboard, matrix liquid-crystal display screen and printer.Working electrode adopts the money base mercury film electrode, and contrast electrode adopts mercurous chloride electrode, and auxiliary electrode adopts platinum electrode, is furnished with stirrer in the electrolytic cell.Scanning voltage controller, potentiostat and current-voltage converter are formed a polarograph.Computer program according to as shown in Figure 2 flowcharting deposits in the memory under program of computing machine, executive program control polarograph is measured, and the working electrode electric current is handled with corresponding scanning voltage input computing machine after being converted into voltage signal.Contain NaCl0.01mol/L, HCl0.01mol/L in the test solution, Zn4 μ g/L, Pb2 μ g/L, Cu8 μ g/L.Test condition: starting potential-1.35V, final voltage-0.05V, voltage scanning speed 200mV/s.As shown in Figure 2, be that 5S, enrichment time FT1 are that 60S, time of repose JT are 158, scavenging period QT2 is that 30S, enrichment time FT2 are 5S with keyboard input computing machine scavenging period QT1, computer scanning time ST is 6.58 with the waver input.Computing machine is calculated the sampling period according to sweep time ST=6.5S and sampling number N=480
。Because starting potential, final voltage and sweep time ST all definite, be 200mV/s so obtain voltage scanning speed.The original state of " parity indicator " in the computing machine is i=1.Start computing machine, the I/O mouth of computing machine sends " cleaning " commencing signal, that is: control is opened stirrer and stirred, and the control polarograph adds final voltage-0.05V between working electrode and test solution, start " timer " among the CPU simultaneously, wait for that scavenging period QT1 is 5S; QT1 arrives when scavenging period, the I/O mouth sends termination " cleaning " signal and " enrichment " commencing signal, that is: the control polarograph adds starting potential-1.35V between working electrode and test solution, restarts " timer " among the CPU simultaneously, waits for that enrichment time FT1 is 60S; FT1 arrives when enrichment time, and the I/O mouth sends termination " enrichment " signal and " leaving standstill " commencing signal, that is: stirrer is turned off in control, stops to stir.Restart " timer " among the CPU simultaneously, wait for that time of repose JT is 15S; JT arrives when time of repose, and the I/O mouth sends termination and " leaves standstill " signal and " scanning " commencing signal, promptly controls polarograph speed with 200mV/8 between working electrode and test solution and scans, and begins to end to final voltage-0.05V from starting potential-1.35V.Simultaneous computer begins sampling, and a sampling period T of the every mistake of computing machine once sampling deposits the working electrode current value under scanning voltage value and this scanning voltage among the figure storage portions MM1 among the RAM at every turn.Behind N point of sampling, the end of scan, this duration enrichment time test period finishes, and obtains a working electrode electric current and deposits among the figure storage portions MM1 among the RAM with the change curve MAP1 of scanning voltage, and pass through the matrix liquid-crystal display screen display graphics.Then the state of " parity indicator " among the RAM of computing machine becomes i=2, and computing machine begins control and lacks enrichment time test period.Scavenging period QT2 in this test period is that 30S, enrichment time FT2 are 5S, and other step is identical with long enrichment time test period.Through too short enrichment time test period, computing machine obtains a working electrode electric current by sampling and deposits among the figure storage portions MM2 among the RAM with the change curve MAP2 of scanning voltage, and by the matrix liquid-crystal display screen display graphics.Just finished a circulation through the short enrichment time of a long enrichment time test period and test period.Because when beginning to test, the state labile of electrode, curve M AP1 that measures and curve M AP2 are also unstable, generally will could stablize through 2 to 4 circulations.Since short enrichment time in test period enrichment of element to be measured less, so short at the scavenging period of long enrichment time in test period a bit with regard to passable (5S), can save Measuring Time like this.Fig. 3 is the 4th change curve MAP1 that circulates in working electrode electric current that long enrichment time obtains in test period with scanning voltage, as can be seen, measure baseline curvature among the figure, the stripping current peak 1 of Zn is beyond recognition, the stripping electric current honeybee 2 of Pb is also not obvious, almost can't measure.Have only the stripping peak 3 of Cu more obvious among Fig. 3.Fig. 4 is the 4th change curve MAP2 that circulates in working electrode electric current that short enrichment time obtains in test period with scanning voltage, and this figure is the curve of a bending because enrichment time is shorter, enrichment of element to be measured seldom, this curve is near measuring baseline.Fig. 3, Fig. 4 are stable, needn't continue circulation, by keyboard input difference figure instruction, computing machine is with the working electrode current subtraction of each same scan voltage correspondence among curve M AP1 and the curve M AP2, obtain the change curve Δ MAP of a new electric current with scanning voltage, Δ MAP as shown in Figure 5, this curve deposits among the figure storage portions MM among the RAM, and shows this curve by matrix liquid-crystal display screen.By the printer numerical value printout that the honeybee among MAP1, MAP2, Δ MAP and the MAP is high.Measure baseline straightening among the Δ MAP as can be seen from Figure 5, the stripping current peak 1,2,3 of Zn, Pb, Cu all clearly is convenient to analytical calculation.Because the peak height of Zn, the Pb among the Δ MAP, the stripping current peak 1,2,3 of Cu and its concentration have the better linearity relation, so can add standard solution, repeat above-mentioned steps by " standard addition method ", the Δ MAP that gets back carries out quantitative Analysis.
Claims (2)
1, a kind of Polarographic anode dissolving-out analysis method, it divides two test periods, and each test period comprises cleaning, enrichment, leaves standstill, scans four steps, it is characterized in that:
(1) enrichment time of one of them test period is shorter, makes metallic ion to be measured electrolysis enrichment on working electrode less, and the working electrode electric current that obtains after the scanning deposits among the RAM of computing machine with the change curve of scanning voltage;
(2) enrichment time of another test period is longer, make metallic ion to be measured electrolysis enrichment on working electrode more, scan with the scanning voltage identical than short test period with enrichment time, the working electrode electric current that obtains after the scanning deposits among the RAM of computing machine with the change curve of scanning voltage;
(3) with computing machine the working electrode electric current that obtains in test period in longer enrichment time is differed from the change curve of scanning voltage with the change curve of scanning voltage and the working electrode electric current that obtains in test period in shorter enrichment time and subtract computing, the curve that obtains after difference subtracts deposits among the RAM of computing machine;
(4) the curve output that obtains after with the output device of computing machine difference being subtracted is carried out analytical calculation to the curve of output.
2, according to the described a kind of Polarographic anode dissolving-out analysis method of claim 1, it is characterized in that adopting the following step:
(1) in the RAM of computing machine, opens up figure storage portions MM1, MM2, MM;
(2) in the RAM of computing machine, open up storage portions, be respectively:
QM1: be used to deposit scavenging period QT1,
QM2: be used to deposit scavenging period QT2,
FM1: be used to deposit enrichment time FT1,
FM2: be used to deposit enrichment time FT2,
JM: be used to deposit time of repose JT,
SM: be used to deposit ST or sampling period T sweep time;
(3) in the RAM of computing machine, open up a field and make " parity indicator ", be used to deposit the i value, i=1 when initial;
(4) by input equipment QT1, QT2, FT1, FT2, JT, ST or T are set and deposit in respectively among storage portions QM1, QM2, FM1, FM2, JM, the SM, wherein FT1 is longer than FT2;
(5) according to sweep time ST value and sampled point number N calculate the sampling period
Or the sampling period T of computing machine is imported in employing in advance;
(6) start computing machine,, be designated as " 1 " under decision QT1, QT2, FT1, FT2, MM1 and MM2 are selected and still be " 2 " according to the currency of i;
(7) the I/O mouth by computing machine sends " cleaning " commencing signal, starts " timer " among the CPU simultaneously, and the stand-by period is QTi;
(8) arrive when the QTi time, the I/O mouth sends termination " cleaning " signal and " enrichment " commencing signal, restarts " timer " among the CPU simultaneously, and the stand-by period is FTi;
(9) arrive when the FTi time, the I/O mouth sends termination " enrichment " signal and " leaving standstill " commencing signal, restarts " timer " among the CPU simultaneously, and the stand-by period is JT;
(10) arrive when the JT time, the I/O mouth sends termination and " leaves standstill " signal and " scanning " commencing signal, starts " counter " among the CPU simultaneously, and counting adds up to N (sampling is always counted);
(11) start " timer " among the CPU simultaneously, the stand-by period is T, when the T time then, close by " timer ", the working electrode signal of input is deposited among the figure storage portions MMi, counter subtracts 1;
(12) if Counter Value is not equal to 0, repeating step (11) if Counter Value equals 0, has drawn the working electrode electric current this moment and has deposited among the figure storage portions MMi with the change curve MAPi of scanning voltage;
03) change i value, even original i=1, i=2 then, if original i=2, i=1 then, repeating step (6) be to (12), goes out the work electrode current at this moment again and deposit among the figure storage portions MMi with the change curve MAPi of scanning voltage;
(14) by the keyboard appointment curve M AP1 and MAP2 are subtracted each other, result curve deposits among the MM, by output device result curve is exported, and the curve of exporting is carried out analytical calculation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94110779A CN1040689C (en) | 1994-09-02 | 1994-09-02 | Polarographic anode dissolving-out analysis method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94110779A CN1040689C (en) | 1994-09-02 | 1994-09-02 | Polarographic anode dissolving-out analysis method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1122002A true CN1122002A (en) | 1996-05-08 |
| CN1040689C CN1040689C (en) | 1998-11-11 |
Family
ID=5034708
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94110779A Expired - Lifetime CN1040689C (en) | 1994-09-02 | 1994-09-02 | Polarographic anode dissolving-out analysis method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1040689C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108088885A (en) * | 2017-11-10 | 2018-05-29 | 中国农业大学 | A kind of heavy metal-polluted soil electrochemical in-situ detecting system and detection method |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1710420A (en) * | 2004-06-18 | 2005-12-21 | 刘文涛 | Anode digestion votammetry |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61153560A (en) * | 1984-12-27 | 1986-07-12 | Toshiba Corp | Analysis of dissolved material |
| JPS61247956A (en) * | 1985-04-26 | 1986-11-05 | Sumitomo Metal Ind Ltd | Analysis of antimony contained in galvanizing film |
-
1994
- 1994-09-02 CN CN94110779A patent/CN1040689C/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108088885A (en) * | 2017-11-10 | 2018-05-29 | 中国农业大学 | A kind of heavy metal-polluted soil electrochemical in-situ detecting system and detection method |
| CN108088885B (en) * | 2017-11-10 | 2020-06-30 | 中国农业大学 | Soil heavy metal electrochemical in-situ detection system and detection method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1040689C (en) | 1998-11-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE69023509T2 (en) | DEVICE AND METHOD FOR PERFORMING ELECTROCHEMILUMINESCENT MEASUREMENTS. | |
| US4917774A (en) | Method for analyzing additive concentration | |
| US4917777A (en) | Method for analyzing additive concentration | |
| Batchelor-McAuley et al. | Correction factors for the analysis of voltammetric peak currents measured using staircase voltammetry | |
| JP2002506531A (en) | Method for measuring additives in electroplating baths | |
| CN1040689C (en) | Polarographic anode dissolving-out analysis method | |
| DE69423018T2 (en) | Process for monitoring cleaning treatment in plating baths | |
| Rotureau et al. | Electroanalytical metal sensor with built-in oxygen filter | |
| DE69412354T2 (en) | Process for monitoring the ion concentration in galvanic baths | |
| Miyama et al. | Electrochemical measurements with a periodically renewable pencil electrode | |
| CN1104334A (en) | Automatic potentiometric titrimeter | |
| Turner et al. | Pulsed voltammetric stripping at the thin-film mercury electrode | |
| CN212964737U (en) | Portable heavy metal detector | |
| Branica et al. | Application of ASV for trace metal speciation: Part VI. A computerized pseudopolarographic system | |
| Kryger et al. | Computerized electroanalysis: Part II1. Multiple scanning and background subtraction, a new technique for stripping analysis | |
| CN1554943A (en) | Method for detecting multiple heavy metal elements simultaneously | |
| Nyokong et al. | Computer‐aided chemistry. Part I: Control of the PAR 273 electrochemical instrument using the IBM 9001 laboratory computer | |
| Tzur et al. | Consecutive titrations under non-equilibrium conditions.: A new mode of automatic titration | |
| Pungor et al. | Automatic Electrochemical Analysis: Part 1 | |
| Thomsen et al. | Programmable analyzer for voltammetric and chronopotentiometric experiments | |
| Jadreško | Simulation of Alternative Differential Multi-pulse Voltammetry. Evaluation of the Electrochemical Reversibility by the Voltammogram Symmetry | |
| Economou et al. | Virtual Instrumentation for Stripping Voltammetry on the Rotating Disk Electrode | |
| Salikhdzhanova et al. | Automation of polarographs and voltammetric analyzers | |
| JP3437677B2 (en) | Voltammetry and equipment used therefor | |
| Brito et al. | Determination of the surface charge density of a mercury electrode by extrusion: a new method for correction of the faradaic component |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |