CN1149719A - Polarographic anodic stripping voltammetry - Google Patents
Polarographic anodic stripping voltammetry Download PDFInfo
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- CN1149719A CN1149719A CN 95118074 CN95118074A CN1149719A CN 1149719 A CN1149719 A CN 1149719A CN 95118074 CN95118074 CN 95118074 CN 95118074 A CN95118074 A CN 95118074A CN 1149719 A CN1149719 A CN 1149719A
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Abstract
In order to overcome the shortages of low accuracy of peak measuring by recording instrument and oscillograph and unable to automatically measure the spectrogram of derivative by computer, the present invention displays the spectrogram through lattice liquid crystal display screen and sets two boundary lines with keyboard on two sides of the stripping signal peak of the measured metal and conducts analysis and calculation for the spectrogram in the measuring area between these two boundary lines to calculate out the height of the stripping current of the measured metal. Said invention features high accuracy of measurement and capable of using computer to conduct automatic measurement for the height of peak of the stripping signal in the derivative spectrogram.
Description
The present invention relates to a kind of Polarographic anodic stripping voltammetry that carries out with polarograph, computing machine, lattice liquid crystal display screen and keyboard.
The principle of Polarographic anodic stripping voltammetry is, at first the metallic ion in the test solution 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 produces oxidation current.Writing task electrode current signal or working electrode electric current are to the single order of time or the second derivative signal change curve with scanning voltage, and this curve also is spectrogram.Because scanning voltage is a linear change in time, so spectrogram also is working electrode current signal or working electrode electric current to the single order of time or second derivative signal curve over time.Sometimes for for the purpose of clear and definite, the working electrode current signal is called conventional spectrogram with the change curve of scanning voltage, the working electrode electric current is called the derivative spectrogram to the single order of time or second derivative signal 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 "), the peak current of this metal appears in this moment, shows the stripping signal peak that just occurs this metal on the spectrogram.The peak height of stripping signal peak is directly proportional with the concentration of metallic ion under certain test condition, can calculate the concentration of institute's metal ion in the test solution by the peak height of measuring metal stripping signal peak.During actual measurement, at first under certain test condition, measure the peak height of the stripping signal peak of tested metal in the test solution.Adopt then " standard addition method ", in test solution, add standard solution, under identical test condition, measure the peak height of the stripping signal peak of tested metal in the test solution again, utilize the peak height of the stripping signal peak of the tested metal that this twice side get, can carry out quantitative test, calculate the concentration of tested metallic ion in the test solution.At present, the measurement to the peak height of the stripping signal peak of tested metallic ion mainly contains three kinds of methods, and first kind is the method that adopts registering instrument to measure, by the registering instrument spectrogram that draws.Measure out the peak height of stripping signal peak then with a yardstick, perhaps utilize the grid number that prints on the recording chart to go out the peak height of stripping signal peak; Second method is the method that adopts oscillograph to measure, and spectrogram is presented on the oscillograph, utilizes grid number on the oscillograph window to go out the peak height of stripping signal peak then.Registering instrument and oscillographic measuring method, because the grid that prints on ruler, the recording chart and the precision of the grid on the oscillograph window are lower, so the error of measuring is bigger, measurement result also is subjected to operator's artificial factor, and these two kinds of method automatization levels are lower, troublesome poeration.The third method is to adopt computing machine to measure automatically, and as shown in Figure 1, a line is drawn at two flex point places of the stripping signal peak of computing machine tested metal in spectrogram, measures the vertical range h from the summit to the line then, with h as peak height.Though this method automaticity is higher, the general more complicated of actual spectrogram, this method are often also measured some unwanted assorted peaks even noise signal as peak value automatically, make the measurement result confusion.Sometimes in order to improve sensitivity and resolution, conventional spectrogram that generally need not be as shown in Figure 1, and with as shown in Figure 2 derivative spectrogram in the derivative spectrogram owing to contain negative peak, the method that adopts the aforementioned calculation machine to measure automatically, can't measure the peak height h in the derivative spectrogram, so just be difficult to the superiority highly sensitive, that resolution is high that the derivative spectrogram is had is combined with the automatic measurement of computing machine.
The objective of the invention is to design a kind of method of spectrogram being carried out the localization analytical calculation, this method can show spectrogram by computing machine on the lattice liquid crystal display screen, and the measurement localization is set in spectrogram with keyboard, make the border, the left and right sides of measuring localization be positioned at the two ends of the stripping signal peak of tested metal, computing machine is found out the maximal value and the minimum value of spectrogram ordinate the spectrogram in measuring localization automatically, thereby obtains the peak height of stripping signal peak.
The object of the present invention is achieved like this, a kind of polarogram stripping voltammetry that adopts polarograph, computing machine, lattice liquid crystal display screen LCD and keyboard to carry out, and keyboard has
Key, keyboard, lattice liquid crystal display screen and polarograph all are connected with computing machine;
In the data memory RAM of computing machine, open up storage portions, be respectively:
DATA: being used to deposit the working electrode current signal of polarograph or working electrode electric current is the raw data of spectrogram to the single order of time or second derivative signal with the change curve of scanning voltage, these raw data are computing machines every the working electrode current value of the resulting a series of polarographs of certain sampling period once sampling or working electrode electric current single order or the second derivative value to the time, and they are deposited by the sampling time order in DATA;
BUFFER:, be used to deposit the reflection that lattice liquid crystal display screen LCD goes up picture that show, row's transferring as the display buffer;
Addr
A left side: be used to deposit localization left side boundary line L
A left sideAbscissa value X
A left side, and deposit an initial value in;
Addr
Right: be used to deposit localization the right boundary line L
RightAbscissa value X
Right, and deposit an initial value in;
Flag: sign, if it equals " left side ", L is being transferred in expression now
A left side, if it equals " right side ", L is being transferred in expression now
Right, initial value is put " left side ";
Bx
Right: the low order end abscissa value MAX that is used to deposit whole indication range;
A Bx left side: the high order end abscissa value MIN that is used to deposit whole indication range;
According to the concrete model establishment slot man subroutine of computing machine and lattice liquid crystal display screen LCD, this program deposits among the memory under program ROM of computing machine, and it can be with the raw data and the L of the spectrogram among the DATA
A left side, L
RightArticle two, straight line carries out the picture composing, and the reflection that forms picture deposits among the BUFFER;
According to the concrete model establishment display subroutine of computing machine and lattice liquid crystal display screen LCD, this program deposits among the memory under program ROM of computing machine, and it can give the value among the BUFFER spectrogram and the L that lattice liquid crystal display screen LCD shows certain space of a whole page one by one
A left side, L
RightArticle two, straight line;
Establishment analytical calculation subroutine, this program can be found out at straight line L
A left sideWith straight line L
RightBetween localization in the maximal value and the minimum value of ordinate of spectrogram, this program deposits among the memory under program ROM of computing machine;
Its special character is, adopts the following step:
(1) in the electrolytic cell of polarograph, adds test solution, starting computer system starts working, when polarograph scans, computing machine every a sampling period to working electrode electric current or working electrode electric current single order or second derivative once sampling to the time, working electrode current signal that obtains or working electrode electric current are that spectrogram deposits among the DATA to the single order of time or second derivative signal with the change curve of scanning voltage;
(2) empty BUFFER, transfer the slot man subroutine, spectrogram among the DATA and L
A left side, L
RightArticle two, straight line carries out the picture composing, with spectrogram and L
A left side, L
RightArticle two, the reflection of the picture of straight line deposits among the BUFFER;
(3) transfer display subroutine, give lattice liquid crystal display screen LCD one by one with the value among the BUFFER and show spectrogram and L
A left side, L
RightArticle two, straight line;
(4) read keyboard:
-whenever press once
Key is judged X
A left sideWhether less than MAX, if X
A left sideLess than MAX X then
A left sideAdd 1 and deposit Addr in
A left sideIn, repeating step (2) is to (4), otherwise repeating step (2) is to (4);
-whenever press once
Key is judged X
A left sideWhether greater than MIN, if X
A left sideGreater than MIN X then
A left side Subtract 1 and deposit Addr in
A left sideIn, important step (2) is to (4), otherwise repeating step (2) is to (4);
-as straight line L
A left sideWhen being transferred to the left margin of stripping signal peak of the tested element in the spectrogram, press
Key, X
A left sideBe identified, the flag value becomes " right side " by " left side ";
-whenever press once
Key is judged X
RightWhether less than MAX, if X
RightLess than MAX X then
RightAdd 1 and deposit Addr in
RightIn, important step (2) is to (4), otherwise repeating step (2) is to (4);
-whenever press once
Key is judged X
RightWhether greater than X
A left side, if X
RightGreater than X
A left side, X then
Right Subtract 1 and deposit Addr in
RightIn, important step (2) is to (4), otherwise repeating step (2) is to (4);
-as straight line L
RightWhen being transferred to the right margin of stripping signal peak of the tested element in the spectrogram, press
Key, X
RightBe identified;
(5) transfer the analytical calculation subroutine, the analytical calculation subroutine is from straight line L
A left sideWith straight line L
RightBetween localization in spectrogram in find out the maximal value y of spectrogram ordinate
Max1, and minimum value y
Min1, and calculate the stripping signal peak height Δ y of tested element
1=y
Max1-y
Min1
(6) pass through the output device of computing machine with Δ y
1Output;
(7) in the test solution of the electrolytic cell of polarograph, add standard solution by " standard addition method ", polarograph is swept when arranging, computing machine every a sampling period to working electrode electric current or working electrode electric current single order or second derivative once sampling to the time, working electrode current signal that obtains or working electrode electric current are that spectrogram deposits among the DATA to the single order of time or second derivative signal with the change curve of scanning voltage;
(8) the new spectrogram of selecting step (7) to obtain is transferred the analytical calculation subroutine, the straight line L that the analytical calculation subroutine is determined from step (4)
A left sideWith straight line L
RightBetween localization in spectrogram in find out the maximal value y of spectrogram ordinate
Max2With minimum value y
Min2, and calculate tested element stripping signal peak height Δ y
2=y
Max2-y
Min2
(9) pass through the output device of computing machine with Δ y
2Output;
(10) according to Δ y
1With Δ y
2And concentration, the volume of the titer that adds carry out quantitative Analysis to the concentration of tested element.
The present invention at first passes through computer sampling, the raw data of spectrogram is deposited in the DATA storage portions of data memory, these raw data are a series of working electrode current value or working electrode electric current to single order or the second derivative value of time, and they are that time sequencing according to sampling deposits among the DATA.Set type through the raw data of spectrogram being carried out picture, on lattice liquid crystal display screen LCD, show spectrogram, the ordinate y of spectrogram is exactly working electrode current value or working electrode electric current single order or the second derivative value to the time, because scanning voltage is a linear change to the time, so the horizontal ordinate x of spectrogram is exactly the scanning voltage value.Can observe the stripping signal peak of tested metal by observation point configuration LCDs LCD, by in the keyboard
Key will be measured the boundary line L of localization
A left sideAnd L
RightBe transferred to the two ends of the stripping signal peak of tested metal.L
A left sideAnd L
RightBe respectively that horizontal ordinate equals X
A left sideAnd X
RightTwo straight lines, i.e. L
A left sideBe X=X
A left side, L
RightBe X=X
RightOn lattice liquid crystal display screen LCD, show L
A left sideAnd L
RightArticle two, straight line is for the operator observes, and their real effect is the horizontal ordinate interval of determining analytical calculation.The analytical calculation subroutine is only at straight line L
A left sideWith straight line L
RightBetween localization in spectrogram is carried out analytical calculation, promptly to horizontal ordinate X
A left sideAnd X
RightBetween the ordinate value of spectrogram compare, find at horizontal ordinate X
A left sideWith X
RightBetween the maximal value y of ordinate value of spectrogram
MaxWith minimum value y
Min, maximal value y
MaxDeduct minimum value y
MinCan obtain the peak height Δ y of stripping signal peak.Because employed analytical calculation localization is identical before and after adopting " standard addition method ", promptly at the L that adopts " standard addition method " front and back
A left sideAnd L
RightThe position identical, so obtaining with under the scan voltage in the maximal value of the ordinate value that adopts the spectrogram that obtains before and after " standard addition method ", minimum value is also obtaining with under the scan voltage.Straight line L
A left sideAnd L
RightJust, adjust L in order to set the localization of analytical calculation
A left side, L
RightSequencing unimportant, also can work out concrete computer program in actual applications, adjust earlier L
RightThe position, L is adjusted in the back
A left sideThe position.L
A left sideWith L
RightParticular location neither be unique, L
A left sideWith L
RightAs long as particular location can make the maximal value of the spectrogram that will measure and minimum value be included in L
A left sideWith L
RightBetween get final product.X
A left sideAnd X
RightInitial value should between the high order end abscissa value MIN of the indication range of lattice liquid crystal display screen LCD and low order end abscissa value MAX, choose.For the ease of observing operation, generally with X
A left sideAnd X
RightInitial value all elect MIN as.
Slot man subroutine of the present invention is at first with the raw data and the L of the spectrogram among the DATA
A left side, L
RightArticle two, straight line carries out the picture composing, forms spectrogram and L
A left side, L
RightArticle two, the reflection of the picture of straight line deposits among the BUFFER, then with L among the BUFFER
A left sideAnd L
RightArticle two, the picture color negate between the straight line, that is: be originally " bright " point become " secretly " point, be originally put " secretly " become " bright " point.Like this after lattice liquid crystal display screen LCD shows, straight line L
A left sideWith straight line L
RightBetween the measurement localization in spectrogram with measure localization outside the color opposite (that is: light and shade is opposite) of spectrogram, at adjustment L
A left sideAnd L
RightThe position time, be convenient to the operator and observe.
If simultaneously several metal ion species in the test solution are measured simultaneously, can adopt following technical solution to realize purpose of the present invention: a kind of polarogram stripping voltammetry that adopts polarograph, computing machine, lattice liquid crystal display screen LCD and keyboard to carry out, keyboard has
Key, keyboard, lattice liquid crystal display screen and polarograph all are connected with computing machine;
In the data memory RAM of computing machine, open up storage portions, be respectively:
DATA: be used to deposit the working electrode current signal of polarograph or working electrode electric current to the single order of time or second derivative signal raw data with the change curve of scanning voltage, these raw data are computing machines every the working electrode current value of the resulting a series of polarographs of certain sampling period once sampling or working electrode electric current single order or the second derivative value to the time, and they are deposited by the sampling time order in DATA;
BUFFER:, be used to deposit the reflection that lattice liquid crystal display screen LCD goes up picture that show, row's transferring as the display buffer;
Addr
Left side i: be used to deposit localization i left side boundary line L
Left side iAbscissa value X
Left side i, and deposit an initial value in, and i=1,2,3......N, N are the integer more than or equal to 1;
Addr
Right i: be used to deposit localization i the right boundary line L
Right iAbscissa value X
Right i, and depositing an initial value in, i=1,2,3......N, N are the integer more than or equal to 1;
Flag: sign, if it equals " left side ", L is being transferred in expression now
Left side i, if it equals " right side ", L is being transferred in expression now
Right i, initial value is put " left side ";
Bx
Right: the low order end abscissa value MAX that is used to deposit whole indication range;
Bx
A left side: the high order end abscissa value MIN that is used to deposit whole indication range;
According to the concrete model establishment slot man subroutine of computing machine and lattice liquid crystal display screen LCD, this program deposits among the memory under program ROM of computing machine, and it can be with the raw data and the L of the spectrogram among the DATA
Left side i, L
Right iArticle two, straight line carries out the picture composing, and the reflection that forms picture deposits among the BUFFER;
According to the concrete model establishment display subroutine of computing machine and lattice liquid crystal display screen LCD, this program deposits among the memory under program ROM of computing machine, and it can give the value among the BUFFER spectrogram and the L that lattice liquid crystal display screen LCD shows certain space of a whole page one by one
Left side i, L
Right iArticle two, straight line;
Establishment analytical calculation subroutine, this program can be found out at straight line L
Left side iWith straight line L
Right iBetween localization in the maximal value and the minimum value of ordinate of spectrogram, this program deposits among the memory under program ROM of computing machine;
Its special character is, adopts the following step:
(1) in the electrolytic cell of polarograph, adds test solution, starting computer system starts working, when polarograph scans, computing machine every a sampling period to working electrode electric current or working electrode electric current single order or second derivative once sampling to the time, working electrode current signal that obtains or working electrode electric current are that spectrogram deposits among the DATA to the single order of time or second derivative signal with the change curve of scanning voltage;
(2) the sequence number i of the analytical calculation localization that is provided with keyboard input desire, i=1,2,3.....N, N are the integer more than or equal to 1;
(3) judge whether i equals 1,,, judge X if i is not equal to 1 if i equals 1 and connects step (4)
A left side (i-1)Whether equal X
Right (i-1), if X
A left side (i-1)Equal X
Right (i-1)Then repeat rapid (2) to (3), if X
A left side (i-1)Be not equal to X
Right (i-1), then:
(4) empty BUFFER, transfer the slot man subroutine, the L of the spectrogram among the DATA and all localization
Left side i, L
Right iArticle two, straight line carries out the picture composing, with the L of spectrogram and all localization
Left side i, L
Right iArticle two, the image of the picture of straight line deposits among the BUFFER;
(5) transfer display subroutine, give the L that lattice liquid crystal display screen LCD shows spectrogram and all localization one by one the value among the BUFFER
Left side i, L
RightArticle two, straight line;
(6) read keyboard:
-whenever press once
Key is judged X
Left side iWhether less than MAX, if X
Left side iLess than MAX X then
Left side iAdd 1 and deposit Addr in
Left side iIn, repeating step (4) is to (6), otherwise repeating step (4) is to (6);
-whenever press once
Key judges whether i equals 1, if i equals 1, judges X
Left side iWhether greater than MIN, if X
Left side iGreater than MIN X then
Left side i Subtract 1 and deposit Addr in
Left side iIn, repeating step (4) is to (6), otherwise repeating step (4) is to (6); If i is not equal to 1, judge X
Left side iWhether greater than X
Right (i-1), if X
Left side iGreater than X
Right (i-1), X then
Left side iSubtract 1 and deposit Addr in
Left side iIn, repeating step (4) is to (6), otherwise repeating step (4) is to (6);
-as straight line L
Left side iWhen being transferred to the left margin of stripping signal peak of the tested element in the spectrogram, press
Key, X
Left side iBe identified, the flag value becomes " right side " by " left side ";
-whenever press once
Key is judged X
Right iWhether less than MAX, if X
Right iLess than MAX X then
Right iAdd 1 and deposit Addr in
Right iIn, repeating step (4) is to (6), otherwise repeating step (4) is to (6);
-whenever press once
Key is judged X
Right iWhether greater than X
Left side i, if X
Right iGreater than X
Left side iX then
Right i Subtract 1 and deposit Addr in
Right iIn, repeating step (4) is to (6), otherwise repeating step (4) is to (6);
-as straight line L
Right iWhen being transferred to the right margin of stripping signal peak of the tested element in the spectrogram, press
Key, X
Right iBe identified, the flag value becomes " left side " by " right side ";
(7) judge X
Right iWhether greater than X
A left side (i+i), if X
Right iGreater than X
A left side (i+1), then localization (i+1), (i+2) ... the X of N
A left side (i+1), X
A left side (i+2)... X
Left side NAnd X
Right (i+1), X
Right (i+2)... X
Right NAll equal X
Right i, and deposit corresponding Addr in
A left side (i+1), Addr
A left side (i+2)... Addr
Left side NAnd Addr
Right (i+1), Addr
Right (i+2)... Addr
Right NIn, connect step (8), otherwise:
(8) transfer the analytical calculation subroutine, the analytical calculation subroutine is from straight line L
Left side iWith straight line L
Right iBetween localization in spectrogram in find out the maximal value y of spectrogram ordinate
Imax1With minimum value y
Imini, and calculate the stripping signal peak height Δ y of tested element
I1=y
Imax1-y
Imini
(9) repeating step (2) is to (8), and the stripping signal peak of all tested elements is all set up the analytical calculation localization, and after calculating the stripping signal peak height of all tested elements, and the output device by computing machine is with Δ y
11, Δ y
21... Δ y
N1Output;
(10) in the test solution of the electrolytic cell of polarograph, add standard solution by " standard addition method ", when polarograph scans, computing machine every a sampling period to working electrode electric current or working electrode electric current single order or second derivative once sampling to the time, working electrode current signal that obtains or working electrode electric current are that spectrogram deposits among the DATA to the single order of time or second derivative signal with the change curve of scanning voltage;
(11) the new spectrogram of selecting step (10) to obtain is transferred the analytical calculation subroutine, the straight line L that the analytical calculation subroutine is determined from step (6)
Left side iWith straight line L
Right iBetween localization in spectrogram in find out the maximal value y of spectrogram ordinate
Imax2With minimum value y
Imin2, and calculate the stripping signal peak height Δ y of all tested elements
I2=y
Imax2-y
Imin2
(12) pass through the output device of computing machine with Δ y
12, Δ y
22... Δ y
N2Output;
(13) according to Δ y
11With Δ y
12, Δ y
21With Δ y
22... Δ y
N1With Δ y
N2And concentration, the volume of the titer that adds carry out quantitative Analysis to the concentration of all tested elements.
L
Left side iAnd L
Right iBe respectively that horizontal ordinate equals X
Left side iAnd X
Right iTwo straight lines, that is: L
Left side iBe X=X
Left side i, L
Right iBe X=X
Right iStraight line L
Left side iAnd L
Right iJust, adjust L in order to set the localization of analytical calculation
Left side i, L
Right iSequencing unimportant, also can work out concrete computer program in actual applications, adjust earlier L
Right iThe position, L is adjusted in the back
Left side iThe position.X
Left side iAnd X
Right iInitial value should between the high order end abscissa value MIN of the indication range of lattice liquid crystal display screen LCD and low order end abscissa value MAX, choose.For the ease of observing operation, generally with X
Left side iAnd X
Right iInitial value all elect MIN as.
Above-mentioned technical solution can be provided with several analytical calculation localization in same spectrogram, simultaneously the stripping signal peak height of several tested metals is measured, the different analytical calculation localization of difference during for the ease of operator's observation point configuration LCDs LCD, slot man subroutine of the present invention are at first with the L of raw data He all localization of the spectrogram among the DATA
Left side i, L
Right iArticle two, straight line carries out the picture composing, forms the L of spectrogram and all localization
Left side i, L
Right iArticle two, the reflection of the picture of straight line deposits among the BUFFER, then with L among the BUFFER
Left side iAnd L
Right iArticle two, the picture color negate between the straight line, promptly be originally " bright " point become " secretly " point, be originally put " secretly " become " bright " point.After lattice liquid crystal display screen LCD showed, color in each localization and the color opposite (being that light and shade is opposite) outside the localization helped the operator and distinguish each different analytical calculation localization like this.
The present invention is used for the anodic stripping voltammetry of polarogarphy, can carry out the localization analytical calculation to spectrogram, thereby draws the peak height of the stripping signal peak of tested metal.Because the horizontal ordinate position of the stripping signal peak of the tested metal that is measured with same set of electrode, in liquid of the same end, under the same test parameter is not subjected to displacement in theory, in the reality test, be not subjected to displacement substantially yet, so to same or, in case choose L according to the position of the stripping signal peak of each tested metal with a kind of test of sample
A left sideAnd L
RightBetween localization after, generally do not need again boundary line L to localization
A left sideAnd L
RightChange.When quantitative Analysis is carried out in utilization " standard addition method ", can make operating process simplify, save a large amount of Measuring Time like this.The present invention is by the analytical calculation subroutine, at the straight line L of setting
A left sideWith straight line L
RightBetween the measurement localization in, ordinate value to spectrogram compares, maximizing and minimum value, deduct the peak height that minimum value obtains tested metal stripping signal peak by maximal value then, the measuring accuracy of its peak height depends on the length (or sampled point what) in the sampling period of computing machine, just can improve measuring accuracy to peak height as long as the sampling period shortens (or sampled point increases).Can overcome like this when adopting registering instrument and oscillograph to measure, because ruler and grid precision are low and the big shortcoming of artificial measuring error.Because the present invention can be provided with the analytical calculation localization easily, can be targetedly the scope of analytical calculation be set according to the position of the stripping signal peak of tested metal, avoid peak height unnecessary in the spectrogram is carried out analytical calculation, particularly help rejecting the assorted peak interference that signal noise causes.In the derivative spectrogram, the stripping signal peak of tested metal contains positive and negative two peaks, and analytical calculation subroutine of the present invention is only analyzed comparison to the ordinate of the spectrogram in the analytical calculation localization that is provided with, and finds out maximum ordinate Y
MaxWith minimum ordinate Y
Min, maximum ordinate and minimum ordinate are subtracted each other the peak height of the stripping signal peak that obtains tested metal, so the present invention also can carry out analytical calculation to the derivative spectrogram that contains negative peak.Because measure, measurement baseline smooth advantage more highly sensitive than having with conventional spectrogram measurement with the derivative spectrogram, just can directly carry out analytical calculation with computing machine after adopting the present invention to the derivative spectrogram, use the derivative spectrogram to measure the superiority that is had and combine, improved the automaticity of the sensitivity and the measurement of polarograph with the automatic measurement of computing machine.After adopting the present invention, the resolution of instrument is reached
Make the peak height in the derivative spectrogram measure is realized fast, accurately, avoided the misjudgment of sum of errors computing machine that artificial measurement causes the position of tested metal stripping signal peak.When particularly several tested metal stripping signal peak heights are measured simultaneously in will be to sample, can several measurement localization be set, calculate the peak height of the stripping signal peak of various tested metals simultaneously, can save a large amount of Measuring Time spectrogram.In addition, because the present invention can be with straight line L
A left sideWith straight line L
RightBetween the measurement localization in the picture color negate, help the operator and observe.When particularly the stripping signal peak height of several metals in the same sample being measured simultaneously, several measurement localization can be set on same spectrogram, the color negate that each measures the picture in the localization helps the operator and distinguishes the border, the left and right sides that each measures localization.
Several technical solution of the present invention recited above is all carried out in this order, at first the spectrogram of test solution is sampled, and the raw data of spectrogram is deposited among the DATA; Second pair of spectrogram is provided with the measurement localization, calculates the peak height and the output of stripping signal peak; The 3rd, in test solution, add standard solution, sampling deposits the raw data of spectrogram among the DATA in; The 4th, in the measurement localization that has set, calculate the peak height of stripping signal peak in the new spectrogram and also export.This order is unimportant in fact, key of the present invention is the measurement localization can be set in spectrogram, and can adopt same measurement localization to resulting two spectrograms before and after adding standard solution, computing machine is calculated the peak height of stripping signal peak in measuring localization with the analytical calculation subroutine.All improvement projects of this spirit are all in protection scope of the present invention according to the present invention.For example: earlier the spectrogram of test solution is sampled, the raw data of spectrogram is deposited among the DATA; Add standard solution again in test solution, sampling also deposits in the raw data of spectrogram among the DATA; In two spectrograms before and after the selection adding standard solution any one is provided with the measurement localization, calculates the peak height of stripping signal peak; In the measurement localization that has set, calculate the peak height of stripping signal peak in another spectrogram; The peak height output that will add the stripping signal peak in two spectrograms that obtain before and after the standard solution at last.According to this technical solution in sequence, also in protection scope of the present invention.
Below in conjunction with accompanying drawing inventive embodiment is described in detail.
Fig. 1 is conventional spectrogram.
Fig. 2 asks the derivative spectrogram that obtains after the first order derivative for the working electrode electric current to the time.
Fig. 3 is the circuit block diagram of device therefor of the present invention.
Fig. 4 is provided with a computer program process flow diagram of measuring localization.
Fig. 5 is the computer program process flow diagram that the four measuring localization is set.
Fig. 6 is to Z
nConventional spectrogram in be provided with measure localization before, the spectrogram that lattice liquid crystal display screen LCD shows.
Fig. 7 is to Z
nConventional spectrogram in be provided with measure localization after, the spectrogram that lattice liquid crystal display screen LCD shows.
Before Fig. 8 measures localization for the derivative spectrogram to Zn, Cd, Pb, Cu is provided with, the spectrogram that lattice liquid crystal display screen LCD shows.
After Fig. 9 measures localization for the derivative spectrogram to Zn, Cd, Pb, Cu is provided with, the spectrogram that lattice liquid crystal display screen LCD shows.
As shown in Figure 3, scanning voltage controller, potentiostat, electrolytic cell, auxiliary electrical The utmost point, reference electrode, working electrode, electric current-electric pressure converter, differentiator, addition Device, compensating network form a polarograph, and the measuring process of polarograph is by computer controlled System, the spectrogram that polarograph obtains is by being stored in the computer behind the computer sampling. Calculate Facility have keyboard, LCD screen LCD and printer, and wherein keyboard hasKey. Keyboard, LCD screen LCD and beat The seal machine all is connected with computer by industrial siding. Data memory RAM at computer In open up storage portions, be respectively:
DATA: be used for depositing the initial data of spectrogram, these initial data are that computer is every Working electrode electricity every the resulting a series of polarographs of certain sampling period once sampling Flow valuve or working electrode electric current be to single order or the second dervative value of time, they Deposit by the sampling time order among the DATA.
BUFFER: as the display buffer, be used for depositing LCD screen LCD The reflection of picture upper demonstration, row's transferring;
Addr
Left i: boundary line, the left side L that is used for depositing localization iLeft iAbscissa value XLeft i, And the high order end abscissa MIN that to deposit an initial value in be whole indication range, i=1,2.. ... .N. Measure localization, Addr if only establish oneLeft i、L
Left iAnd XLeft iBe respectively AddrLeft、L
LeftAnd XLeft；
Addr
Right i: boundary line, the right L that is used for depositing localization iRight iAbscissa value XRight i, And the high order end abscissa MIN that to deposit an initial value in be whole indication range, i=1,2.. ... .N. Measure localization, Addr if only establish oneRight i、L
Right iAnd XRight iBe respectively AddrRight、L
RightAnd XRight；
Flag: sign, if it equals " left side ", L is being transferred in expression nowLeft iIf (when only establishing a measurement localization, be LLeft), if it equals " right side ", L is being transferred in expression nowRight iIf (when only establishing a measurement localization, be LRight). Initial value is put " left side ";
B
The x right side: the low order end abscissa value MAX that is used for depositing whole indication range;
B
An X left sideBe used for depositing the high order end abscissa value MIN of whole indication range;
Concrete model establishment slot man according to computer and LCD screen Subprogram, this program deposit among the memory under program ROM of computer. It can be with spectrogram Initial data and the L of all localizationLeft i(or LLeft)、L
Right i(or LRight) two straight lines carry out picture and set type, and form the L of spectrogram and all localizationLeft i(or LLeft)、L
Right i(or LRight) reflection of picture of two straight lines deposits among the BUFFER, then with L among the BUFFERLeft i(or LLeft) and LRight i(or LRight) picture color negate between two straight lines, Namely originally be " bright " point become " secretly " point, be becoming of putting " secretly " originally " bright " point.
Concrete model establishment display subroutine according to computer and LCD screen LCD, this program deposits among the memory under program ROM of computer, and it can give the value among the BUFFER spectrogram and the L that LCD screen LCD shows certain space of a whole page one by oneLeft i(or LLeft)、L
Right i(or LRight) two straight lines.
Establishment analytical calculation subprogram, this program can be to straight line LLeft i(or LLeft) and straight line LRight i(or LRight) between localization in the ordinate of spectrogram compare, find out maximum y whereinmaxWith minimum of a value ymin, and calculate Δ y=ymax-y
min This program Deposit among the memory under program ROM of computer;
Embodiment 1: present embodiment is used for measuring the concentration of test solution Zn, can only be provided with one in the computer program and measure localization.
(1) in the electrolytic cell of polarograph, adds test solution, starting computer system starts working, when polarograph scans, computing machine every a sampling period to the working electrode current sample once, the working electrode electric current that obtains is that conventional spectrogram deposits among the DATA with the change curve of scanning voltage.The spectrogram that deposits among the DATA is to obtain with post-sampling at the in stable condition of electrode.The horizontal ordinate of spectrogram is a scanning voltage, and ordinate is the working electrode electric current.
As shown in Figure 4, computing machine follows these steps to operation:
(2) empty BUFFER, transfer the slot man subroutine, spectrogram among the DATA and L
A left side, L
RightArticle two, straight line carries out the picture composing, with spectrogram and L
A left side, L
RightArticle two, the reflection of the picture of straight line deposits among the BUFFER;
(3) transfer display subroutine, give lattice liquid crystal display screen LCD one by one with the value among the BUFFER and show spectrogram and L
A left side, L
RightArticle two, straight line.
At this moment, lattice liquid crystal display screen LCD goes up the spectrogram that shows as shown in Figure 6, and 1 is the stripping current peak of Zn in the spectrogram, straight line L
A left sideAnd L
RightHigh order end at lattice liquid crystal display screen LCD overlaps.
(4) read keyboard:
-whenever press once
Key is judged X
A left sideWhether less than MAX.If X
A left sideLess than MAX, X then
A left sideAdd 1 and deposit Addr in
A left sideIn, then judge X
RightWhether less than X
A left side, if X
RightLess than X
A left side, X then
Right=X
A left sideDeposit in the Addr right side, repeating step (2) is to (4); If X
RightBe not less than X
A left side, repeating step (2) is to (4).If X
A left sideBe not less than MAX, repeating step (2) is to (4);
L in this process
A left sideAdjusted L to the right
RightAlso follow L
A left sideAdjusted to the right together.
-whenever press once
Key is judged X
A left sideWhether greater than MIN, if X
A left sideGreater than MIN, X then
A left sideSubtract 1 and deposit Addr in
A left sideIn, repeating step (2) is to (4); Otherwise, if X
A left sideBe not more than MIN, repeating step (2) is to (4);
In this process, L
A left sideAdjusted left, be mainly used in and work as L
A left sideTransfer to the right excessive after, use
Key is recalled to the origin-location with it again.
-as straight line L
A left sideWhen being transferred to the left margin of stripping current peak 1 of the Zn in the spectrogram, press
Key, X
A left sideBe identified, the flag value becomes " right side " by " left side ";
This process will be measured boundary line, the left side L of localization
A left sideConfirm, later on no longer change.
-whenever press once
Key is judged X
RightWhether less than MAX, if X
RightLess than MAX, X then
RightAdd 1 and deposit Addr in
RightIn, repeating step (2) is to (4); Otherwise, if X
RightBe not less than MAX, then repeating step (2) is to (4);
In this process, L
RightAdjusted to the right.
-whenever press once
Key is judged X
RightWhether greater than X
A left side, if X
RightGreater than X
A left side, X then
RightSubtract 1 and deposit Addr in
RightIn, repeating step (2) is to (4); Otherwise, if X
RightBe not more than X
A left side, then repeating step (2) is to (4);
In this process, L
RightAdjusted left.
-as straight line L
RightWhen being transferred to the right margin of stripping current peak 1 of the Zn in the spectrogram, press
Key, X
RightBe identified;
This process will be measured boundary line, the right L of localization
RightConfirm, later on no longer change.That lattice liquid crystal display screen LCD shows, as to mix up measurement localization spectrogram as shown in Figure 7.
(5) transfer the analytical calculation subroutine, the analytical calculation subroutine is with the X that is identified
A left sideAnd X
RightBetween the ordinate of spectrogram compare, find out X
A left sideAnd X
RightBetween the maximal value y of ordinate of spectrogram
Max1With minimum value y
Min1, and the peak height Δ y that calculates the stripping current peak of Zn
1=y
Max1-y
Min1, and deposit in the corresponding storage portions;
(6) by printer with Δ y
1Printout;
(7) in the test solution of the electrolytic cell of polarograph, add the standard solution of Zn by " standard addition method ", when polarograph scans, computing machine every a sampling period to the working electrode current sample once, the working electrode electric current that obtains is that conventional spectrogram deposits among the DATA with the change curve of scanning voltage.The spectrogram that deposits among the DATA is to obtain with post-sampling at the in stable condition of electrode.The horizontal ordinate of spectrogram is a scanning voltage, and ordinate is the working electrode electric current;
(8) the new spectrogram of selecting step (7) to obtain is transferred the analytical calculation subroutine, the straight line L that the analytical calculation subroutine is determined step (4)
A left sideWith straight line L
RightBetween localization in spectrogram carry out analytical calculation, i.e. the X that step (4) is determined
A left sideWith X
RightBetween the ordinate of spectrogram compare, find out X
A left sideAnd X
RightBetween the maximal value y of ordinate of spectrogram
Max2With minimum value y
Min2, and the peak height Δ y that calculates the stripping current peak of Zn
2=y
Max2-y
Min2
(9) by printer with Δ y
2Printout;
(10) according to Δ y
1With Δ y
ZAnd concentration, the volume of the titer of the Zn that adds carry out quantitative Analysis to the concentration of Zn.
Embodiment 2: present embodiment is mainly used in to be measured simultaneously to the Zn in the test solution, Cd, four kinds of metals of Pb, Cu, in the computer program four measuring localization can be set.
(1) in the electrolytic cell of polarograph, adds test solution, starting computer system starts working, when polarograph scans, computing machine every a sampling period to the first order derivative once sampling of working electrode electric current to the time, the working electrode electric current that obtains is that the raw data of derivative spectrogram deposits among the DATA to the first order derivative of time with the change curve of scanning voltage.The derivative spectrogram that deposits among the DATA is to obtain with post-sampling at the in stable condition of electrode.The horizontal ordinate of derivative spectrogram is a scanning voltage, and ordinate is the first order derivative of working electrode electric current to the time.Differentiate to the working electrode electric current is to finish by differentiator.
As shown in Figure 5, computing machine follows these steps to operation:
(2) the sequence number i of the analytical calculation localization that is provided with keyboard input desire, i=1,2,3,4, input sequence number 1 earlier here;
(3) judge whether i equals 1, if i equals 1 and connects step (4); If i is not equal to 1, judge X
A left side (i-1)Whether equal X
Right (i-1), if X
A left side (i-1)Equal X
Right (i-1), then repeating step (2) is to (3), if X
A left side (i-1)Be not equal to X
Right (i-1), then: connect step (4);
Selected analytical calculation localization sequence number i is 1 in the step (2), so directly enter step (4) after judgement i is 1 in step (3).Judge X
A left side (i-1)Whether equal X
Right (i-1)Being mainly used in the left side of seeing selected analytical calculation localization sequence number i has the analytical calculation localization that endlessly sets, if do not have then the value of gravity treatment sequence number i.
(4) empty BUFFER, transfer the slot man subroutine, the L of the derivative spectrogram among the DATA and all localization
Left side i, L
Right iArticle two, straight line carries out the picture composing, with the L of derivative spectrogram and all localization
Left side i, L
Right iArticle two, the image of the picture of straight line deposits among the BUFFER;
(5) transfer display subroutine, give the L that lattice liquid crystal display screen LCD shows derivative spectrogram and all localization one by one the value among the BUFFER
Left side i, L
Right iArticle two, straight line;
At this moment, lattice liquid crystal display screen LCD goes up the derivative spectrogram that shows as shown in Figure 8, and peak 1,2,3,4 is respectively the stripping current peak of Zn, Cd, Pb, Cu, straight line L in the derivative spectrogram
Left side iAnd L
Right iHigh order end at lattice liquid crystal display screen LCD overlaps.
(6) read keyboard:
---whenever press once
Key is judged X
Left side iWhether less than MAX, if less than MAX, X then
A left side 1Add 1 and deposit Addr in
A left side 1In, judge X
A left side 1Whether greater than X
Right 1, if X
A left side 1Greater than X
Right 1, X then
Right 1=X
A left side 1Deposit Addr in
Right 1In, if X
A left side 1Be not more than X
Right 1, then repeating step (4) is to (6); If X
A left side 1Be not less than MAX, then repeating step (4) is to (6);
-whenever press once
Key is judged: whether equal 1, if i equals 1 (equaling I this moment), judge X
A left side 1Whether greater than MIN, if X
A left side 1Greater than MIN, X then
A left side 1Subtract 1 and deposit Addr in
A left side 1In, repeating step (4) is to (6); If X
A left side 1Be not more than MIN, then repeating step (4) is to (6); If i is not equal to 1, judge X
A left side 1Whether greater than X
Right (i-1), if X
A left side 1Greater than X
Right (i-1), X then
A left side 1Equal X
A left side 1Subtract 1 and deposit Addr in
A left side 1In, repeating step (4) is to (6).If X
A left side 1Be not more than X
Right (i-1), then repeating step (4) is to (6);
-as straight line L
A left side 1When being transferred to the left side at stripping electric current derivative peak 1 of Zn in the derivative spectrogram, press
Key, X
A left side 1Be identified, the flag value becomes " right side " by " left side ";
-whenever press
Key is judged X
Right 1Whether less than MAX, if X
Right 1Less than MAX, X then
Right 1Add 1 and deposit Addr in
Right 1In, important step (4) is to (6), otherwise repeating step (4) is to (6);
-whenever press once
Key is judged X
Right 1Whether greater than X
A left side 1, if X
Right 1Greater than X
A left side 1, X then
Right 1Subtract 1 and deposit Addr in
Right 1In, repeating step (4) is to (6), otherwise repeating step (4) is to (6);
-as straight line L
Right 1When being transferred to the right side at stripping electric current derivative peak 1 of the Zn in the derivative spectrogram, press
Key, X
Right 1Be identified, the flag value becomes " left side " by " right side ";
Determine L
A left side 1With L
Right 1Particular location the time, as long as can make by L
A left side 1With L
Right 1The summit of the posivtive spike at the stripping electric current derivative peak 1 of the tested Metal Zn in the measurement localization that is limited is that the peak valley of maximal value, negative peak is that minimum value gets final product.
(7) judge X
Right 1Whether greater than X
A left side 2, if X
Right 1Greater than X
A left side 2, the X of localization 2,3,4 then
A left side 2, X
A left side 3, X
A left side 4, X
Right 2, X
Right 3, X
Right 4All equal X
Right 1, and deposit corresponding Addr in
A left side 2, Addr
A left side 3, Addr
A left side 4, Addr
Right 2, Addr
Right 3, Addr
Right 4In, connect step (8); If X
Right 1Be not more than X
A left side 2, then:
(8) transfer the analytical calculation subroutine, the analytical calculation subroutine is from straight line L
A left side 1With straight line L
Right 1Between localization 1 in the derivative spectrogram in, to X
A left side 1With X
Right 1Between the ordinate of derivative spectrogram compare, find out maximum ordinate y
1max1With minimum ordinate y
1min1, and calculate the derivative peak height Δ y of the stripping electric current of Zn
11=y
1max1-y
1min1, deposit in the corresponding storage portions;
(9) repeating step (2) is to (8), and the both sides at the stripping electric current derivative peak 2,3,4 of Cd, Pb, Cu are provided with analytical calculation localization 2,3,4 respectively, and the peak height of calculating the stripping electric current derivative peak of Cd, Pb, Cu is respectively Δ y
21, Δ y
31, Δ y
41, by printer with Δ y
11, Δ y
21, Δ y
31, Δ y
41Printout;
At this moment, lattice liquid crystal display screen LCD goes up derivative spectrogram and the straight line L that shows
A left side 1, L
Right 1, L
A left side 2, L
Right 2, L
A left side 3, L
Right 3, L
A left side 4, L
Right 4As shown in Figure 9.
(10) in the test solution of the electrolytic cell of polarograph, add the standard solution of Zn, Cd, Pb, Cu by " standard addition method ".When polarograph scans, computing machine every a sampling period to the first order derivative once sampling of working electrode electric current to the time, the working electrode electric current that obtains is that the raw data of derivative spectrogram deposits among the DATA to the first order derivative of time with the change curve of scanning voltage.The derivative spectrogram that deposits among the DATA is to obtain with post-sampling at the in stable condition of electrode.The horizontal ordinate of derivative spectrogram is a scanning voltage, and ordinate is the first order derivative of working electrode electric current to the time.
(11) the new derivative spectrogram of selecting step (10) to obtain is transferred the analytical calculation subroutine, the straight line L that the analytical calculation subroutine is determined from step (6)
A left side 1With L
Right 1Between, L
A left side 2With L
Right 2Between, L
A left side 3With L
Right 3Between, L
A left side 4With L
Right 4Between localization 1, localization 2, localization 3, localization 4 in the derivative spectrogram in, find out the maximal value y of the ordinate of spectrogram respectively
1max2, y
2max2, y
3max2And y
4max2, minimum value y
1min2, y
2min2, y
3min2And y
4min2, and calculate the peak height Δ y at the stripping electric current derivative peak of Zn, Cd, Pb, Cu
12=y
1max2-y
1min2, Δ y
22=y
2max2-y
2min2, Δ y
32=y
3max2-y
3min2, Δ y
42=y
4max2-y
4min2, and deposit in the corresponding storage portions;
(12) by printer with Δ y
12, Δ y
22, Δ y
32, Δ y
42Output;
(13) according to Δ y
11With Δ y
12, Δ y
21With Δ y
22, Δ y
31With Δ y
32, Δ y
41With Δ y
42And concentration, the volume of the titer of the Zn, the Cd that add, Pb, Cu carry out quantitative Analysis to the concentration of Zn, Cd, Pb, Cu.
Claims (4)
1. polarogram stripping voltammetry that adopts polarograph, computing machine, lattice liquid crystal display screen LCD and keyboard to carry out, keyboard has
Key, keyboard, lattice liquid crystal display screen and polarograph all are connected with computing machine;
In the data memory RAM of computing machine, open up storage portions, be respectively:
DATA: being used to deposit the working electrode current signal of polarograph or working electrode electric current is the raw data of spectrogram to the single order of time or second derivative signal with the change curve of scanning voltage, these raw data are computing machines every the working electrode current value of the resulting a series of polarographs of certain sampling period once sampling or working electrode electric current single order or the second derivative value to the time, and they are deposited by the sampling time order in DATA;
BUFFER:, be used to deposit the reflection that lattice liquid crystal display screen LCD goes up picture that show, row's transferring as the display buffer;
Addr
A left side: be used to deposit localization left side boundary line L
A left sideAbscissa value X
A left side, and deposit an initial value in;
Addr
Right: be used to deposit localization the right boundary line L
RightAbscissa value X
Right, and deposit an initial value in;
Flag: sign, if it equals " left side ", L is being transferred in expression now
A left side, if it equals " right side ", L is being transferred in expression now
Right, initial value is put " left side ";
Bx
Right: the low order end abscissa value MAX that is used to deposit whole indication range;
Bx
A left side: the high order end abscissa value MIN that is used to deposit whole indication range;
According to the concrete model establishment slot man subroutine of computing machine and lattice liquid crystal display screen LCD, this program deposits among the memory under program ROM of computing machine, and it can be with the raw data and the L of the spectrogram among the DATA
A left side, L
RightArticle two, straight line carries out the picture composing, and the reflection that forms picture deposits among the BUFFER;
According to the concrete model establishment display subroutine of computing machine and lattice liquid crystal display screen LCD, this program deposits among the memory under program ROM of computing machine, and it can give the value among the BUFFER spectrogram and the L that lattice liquid crystal display screen LCD shows certain space of a whole page one by one
A left side, L
RightArticle two, straight line;
Establishment analytical calculation subroutine, this program can be found out at straight line L
A left sideWith straight line L
RightBetween localization in the maximal value and the minimum value of ordinate of spectrogram, this program deposits among the memory under program ROM of computing machine;
It is characterized in that, adopt the following step:
(1) in the electrolytic cell of polarograph, adds test solution, starting computer system starts working, when polarograph scans, computing machine every a sampling period to working electrode electric current or working electrode electric current single order or second derivative once sampling to the time, working electrode current signal that obtains or work electroplax electric current deposit among the DATA the single order of time or the second derivative signal change curve collection of impressions of seals by famous seal figure with scanning voltage;
(2) empty BUFFER, transfer the slot man subroutine, spectrogram among the DATA and L
A left side, L
RightArticle two, straight line carries out the picture composing, with spectrogram and L
A left side, L
RightArticle two, the reflection of the picture of straight line deposits among the BUPFER;
(3) transfer display subroutine, give lattice liquid crystal display screen LCD one by one with the value among the BUFFER and show spectrogram and L
A left side, L
RightArticle two, straight line;
(4) read keyboard:
-whenever press once
Key is judged X
A left sideWhether less than MAX, if X
A left sideLess than MAX X then
A left sideAdd 1 and deposit an Addr left side in
In, repeating step (2) is to (4), otherwise repeating step (2) is to (4);
-whenever press once
Key is judged X
A left sideWhether greater than MIN, if X
A left sideGreater than MIN X then
A left sideSubtract 1 and deposit an Addr left side in
In, important step (2) is to (4), otherwise repeating step (2) is to (4);
-as straight line L
A left sideWhen being transferred to the left margin of stripping signal peak of the tested element in the spectrogram, press
Key, X
A left sideBe identified, the flag value becomes " right side " by " left side ";
-whenever press once
Key is judged X
RightWhether less than MAX, if X
RightLess than MAX X then
RightAdd 1 and deposit Addr in
RightIn, important step (2) is to (4), otherwise repeating step (2) is to (4);
-whenever press once
Key is judged X
RightWhether greater than X
A left side, if X
RightGreater than X
A left side, X then
RightSubtract 1 and deposit Addr in
RightIn, important step (2) is to (4), otherwise repeating step (2) is to (4);
-as straight line L
RightWhen being transferred to the right margin of stripping signal peak of the tested element in the spectrogram, press
Key, X
RightBe identified;
(5) transfer the analytical calculation subroutine, the analytical calculation subroutine is from straight line L
A left sideWith straight line L
RightBetween localization in spectrogram in find out the maximal value y of spectrogram ordinate
Max1With minimum value y
Min1, and calculate the stripping signal peak height Δ y of tested element
1=y
Max1-y
Min1
(6) pass through the output device of computing machine with Δ y
1Output;
(7) in the test solution of the electrolytic cell of polarograph, add standard solution by " standard addition method ", when polarograph scans, computing machine every a sampling period to working electrode electric current or working electrode electric current single order or second derivative once sampling to the time, working electrode current signal that obtains or working electrode electric current are that spectrogram deposits among the DATA to the single order of time or second derivative signal with the change curve of scanning voltage;
(8) the new spectrogram of selecting step (7) to obtain is transferred the analytical calculation subroutine, the straight line L that the analytical calculation subroutine is determined from step (4)
A left sideWith straight line L
RightBetween localization in spectrogram in find out the maximal value y of spectrogram ordinate
Max2With minimum value y
Min2, and calculate tested element stripping signal peak height Δ y
2=y
Max2-y
Min2
(9) pass through the output device of computing machine with Δ y
2Output;
(10) according to Δ y
1With Δ y
2And concentration, the volume of the titer that adds carry out quantitative Analysis to the concentration of tested element.
2. according to the described a kind of polarogram stripping voltammetry that adopts polarograph, computing machine, lattice liquid crystal display screen LCD and keyboard to carry out of claim 1, it is characterized in that the slot man subroutine is at first with the raw data and the L of the spectrogram among the DATA
A left side, L
RightArticle two, straight line carries out the picture composing, forms spectrogram and L
A left side, L
RightArticle two, the reflection of the picture of straight line deposits among the BUFFER, then with L among the BUFFER
A left sideAnd L
RightArticle two, the picture color negate between the straight line, that is: be originally " bright " point become " secretly " point, be originally put " secretly " become " bright " point.
3. polarogram stripping voltammetry that adopts polarograph, computing machine, lattice liquid crystal display screen LCD and keyboard to carry out, keyboard has
Key, keyboard, lattice liquid crystal display screen and polarograph all are connected with computing machine;
In the data memory RAM of computing machine, open up storage portions, be respectively:
DATA: be used to deposit the working electrode current signal of polarograph or working electrode electric current to the single order of time or second derivative signal raw data with the change curve of scanning voltage, these raw data are computing machines every the working electrode current value of the resulting a series of polarographs of certain sampling period once sampling or working electrode electric current single order or the second derivative value to the time, and they are deposited by the sampling time order in DATA;
BUEFER:, be used to deposit the reflection that lattice liquid crystal display screen LCD goes up picture that show, row's transferring as the display buffer;
Addr
Left side i: be used to deposit localization i left side boundary line L
Left side iAbscissa value X
Left side i, and deposit an initial value in, and i=1,2,3......N, N are the integer more than or equal to 1;
Addr
Right i: be used to deposit localization i the right boundary line L
Right iAbscissa value X
Right i, and depositing an initial value in, i=1,2,3......N, N are the integer more than or equal to 1;
Flag: sign, if it equals " left side ", L is being transferred in expression now
Left side i, if it equals " right side ", L is being transferred in expression now
Right i, initial value is put " left side ";
Bx
Right: the low order end abscissa value MAX that is used to deposit whole indication range;
Bx
A left side: the high order end abscissa value MIN that is used to deposit whole indication range;
According to the concrete model establishment slot man subroutine of computing machine and lattice liquid crystal display screen LCD, this program deposits among the memory under program ROM of computing machine, and it can be with the raw data and the L of the spectrogram among the DATA
Left side i, L
Right iArticle two, straight line carries out the picture composing, and the reflection that forms picture deposits among the BUFFER;
According to the concrete model establishment display subroutine of computing machine and lattice liquid crystal display screen LCD, this program deposits among the memory under program ROM of computing machine, and it can give the value among the BUFFER spectrogram and the L that lattice liquid crystal display screen LCD shows certain space of a whole page one by one
Left side i, L
Right iArticle two, straight line;
Establishment analytical calculation subroutine, this program can be found out at straight line L
Left side iWith straight line L
Right iBetween localization in the maximal value and the minimum value of ordinate of spectrogram, this program deposits among the memory under program ROM of computing machine;
It is characterized in that, adopt the following step:
(1) in the electrolytic cell of polarograph, adds test solution, starting computer system starts working, when polarograph scans, computing machine every a sampling period to working electrode electric current or working electrode electric current single order or second derivative once sampling to the time, working electrode current signal that obtains or working electrode electric current are that spectrogram deposits among the DATA to the single order of time or second derivative signal with the change curve of scanning voltage;
(2) the sequence number i of the analytical calculation localization that is provided with keyboard input desire, i=1,2,3......N, N are the integer more than or equal to 1;
(3) judge whether i equals 1,,, judge X if i is not equal to 1 if i equals 1 and connects step (4)
(i-1)Whether equal X
Right (i-1), if X
A left side (i-1)Equal X
Right (i-1)Then repeating step (2) is to (3), if X
A left side (i-1)Be not equal to X
Right (i-1), then:
(4) empty BUEFER, transfer the slot man subroutine, the L of the spectrogram among the DATA and all localization
Left side i, L
Right iArticle two, straight line carries out the picture composing, with the L of spectrogram and all localization
Left side i, L
Right iArticle two, the image of the picture of straight line deposits among the BUFFER;
(5) transfer display subroutine, give the L that lattice liquid crystal display screen LCD shows spectrogram and all localization one by one the value among the BUFFER
Left side i, L
Right iArticle two, straight line;
(6) read keyboard:
-whenever press once
Key is judged X
Left side iWhether less than MAX, if X
Left side iLess than MAX X then
Left side iAdd 1 and deposit Addr in
Left side iIn, repeating step (4) is to (6), otherwise repeating step (4) is to (6);
-whenever press once
Key judges whether i equals 1, if i equals 1, judges X
Left side iWhether greater than MIN, if X
Left side iGreater than MIN X then
Left side iSubtract 1 and deposit Addr in
Left side iIn, repeating step (4) is to (6), otherwise repeating step (4) is to (6); If i is not equal to 1, judge X
Left side iWhether greater than X
Right (i-1), if X
Left side iGreater than X
Right (i-1), X then
Left side iSubtract 1 and deposit Addr in
Left side iIn, repeating step (4) is to (6), otherwise repeating step (4) is to (6);
-as straight line L
Left side iWhen being transferred to the left margin of stripping signal peak of the tested element in the spectrogram, press
Key, X
Left side iBe identified, the flag value becomes " right side " by " left side ";
-whenever press once
Key is judged X
Right iWhether less than MAX, if X
Right iLess than MAX X then
Right iAdd 1 and deposit Addr in
Right iIn, repeating step (4) is to (6), otherwise repeating step (4) is to (6);
-whenever press once
Key is judged X
Right iWhether greater than X
Left side i, if X
Right iGreater than X
Left side iX then
Right iSubtract 1 and deposit Addr in
Right iIn, repeating step (4) is to (6), otherwise repeating step (4) is to (6);
-as straight line L
Right iWhen being transferred to the right margin of stripping signal peak of the tested element in the spectrogram, press
Key, X
Right iBe identified, the flag value becomes " left side " by " right side ";
(7) judge X
Right iWhether greater than X
A left side (i+1), if X
Right iGreater than X
A left side (i+1), then localization (i+1), (i+2) ... the X of N
A left side (i+1), X
A left side (i+2)... X
Left side NAnd X
Right (i+1), X
Right (i+2)... X
Right NAll equal X
Right i, and deposit corresponding Addr in
A left side (i+1), Addr
A left side (i+2)... Addr
Left side NAnd Addr
Right (i+1), Addr
Right (i+2)... Addr
Right NIn, connect step (8), otherwise:
(8) transfer the analytical calculation subroutine, the analytical calculation subroutine is from straight line L
Left side iWith straight line L
Right iBetween localization in spectrogram in find out the maximal value y of spectrogram ordinate
Imax1With minimum value y
Imin1, and calculate the stripping signal peak height Δ y of tested element
I1=y
Imax1-y
Imin1
(9) repeating step (2) is to (8), and the stripping signal peak of all tested elements is all set up the analytical calculation localization, and after calculating the stripping signal peak height of all tested elements, and the output device by computing machine is with Δ y
11, Δ y
21... Δ y
N1Output;
(10) in the test solution of the electrolytic cell of polarograph, add standard solution by " standard addition method ", when polarograph scans, computing machine every a sampling period to working electrode electric current or working electrode electric current single order or second derivative once sampling to the time, working electrode current signal that obtains or working electrode electric current are that spectrogram deposits among the DATA to the single order of time or second derivative signal with the change curve of scanning voltage;
(11) the new spectrogram of selecting step (10) to obtain is transferred the analytical calculation subroutine, the straight line L that the analytical calculation subroutine is determined from step (6)
Left side iWith straight line L
Right iBetween localization in spectrogram in find out the maximal value y of spectrogram ordinate
Imax2With minimum value y
Imin2, and calculate the stripping signal peak height Δ y of all tested elements
I2=y
Imax2-y
Imin2
(12) pass through the output device of computing machine with Δ y
12, Δ y
22... Δ y
N2Output;
(13) according to Δ y
11With Δ y
12, Δ y
21With Δ y
22... Δ y
N1With Δ y
N2And concentration, the volume of the titer that adds carry out quantitative Analysis to the concentration of all tested elements.
4. according to the described a kind of polarogram stripping voltammetry that adopts polarograph, computing machine, lattice liquid crystal display screen LCD and keyboard to carry out of claim 3, it is characterized in that the slot man subroutine is at first with the L of raw data He all localization of the spectrogram among the DATA
Left side i, L
Right iArticle two, straight line carries out the picture composing, forms the L of spectrogram and all localization
Left side i, L
Right iArticle two, the reflection of the picture of straight line deposits among the BUFFER, then with L among the BUFFER
Left side iAnd L
Right iArticle two, the picture color negate between the straight line, promptly be originally " bright " point become " secretly " point, be originally put " secretly " become " bright " point.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95118074 CN1149719A (en) | 1995-11-05 | 1995-11-05 | Polarographic anodic stripping voltammetry |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95118074 CN1149719A (en) | 1995-11-05 | 1995-11-05 | Polarographic anodic stripping voltammetry |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1149719A true CN1149719A (en) | 1997-05-14 |
Family
ID=5081563
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 95118074 Pending CN1149719A (en) | 1995-11-05 | 1995-11-05 | Polarographic anodic stripping voltammetry |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1149719A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1981192B (en) * | 2004-05-14 | 2014-04-16 | 拜尔健康护理有限责任公司 | Voltammetric systems for assaying biological analytes |
-
1995
- 1995-11-05 CN CN 95118074 patent/CN1149719A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1981192B (en) * | 2004-05-14 | 2014-04-16 | 拜尔健康护理有限责任公司 | Voltammetric systems for assaying biological analytes |
| CN103901092B (en) * | 2004-05-14 | 2016-07-06 | 拜尔健康护理有限责任公司 | The voltammertry system of detection biological analyte |
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