CN1149719A - Polarographic anodic stripping voltammetry - Google Patents

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

Polarographic anodic stripping voltammetry

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 side}Abscissa 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 side}With 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 side}Whether less than MAX, if X_{A left side}Less than MAX X then_{A left side}Add 1 and deposit Addr in_{A left side}In, repeating step (2) is to (4), otherwise repeating step (2) is to (4);

-whenever press once

Key is judged X_{A left side}Whether greater than MIN, if X_{A left side}Greater than MIN X then_{A left side}Subtract 1 and deposit Addr in_{A left side}In, important step (2) is to (4), otherwise repeating step (2) is to (4);

-as straight line L_{A left side}When being transferred to the left margin of stripping signal peak of the tested element in the spectrogram, pressKey, X_{A left side}Be identified, the flag value becomes " right side " by " left side ";

-whenever press onceKey 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, pressKey, X_RightBe identified;

(5) transfer the analytical calculation subroutine, the analytical calculation subroutine is from straight line L_{A left side}With 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 element₁=y_Max1-y_Min1

(6) pass through the output device of computing machine with Δ y₁Output;

(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 side}With 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 y₂=y_Max2-y_Min2

(9) pass through the output device of computing machine with Δ y₂Output;

(10) according to Δ y₁With Δ y₂And 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 side}And L_RightBe transferred to the two ends of the stripping signal peak of tested metal.L_{A left side}And L_RightBe respectively that horizontal ordinate equals X_{A left side}And X_RightTwo straight lines, i.e. L_{A left side}Be X=X_{A left side}, L_RightBe X=X_RightOn lattice liquid crystal display screen LCD, show L_{A left side}And 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 side}With straight line L_RightBetween localization in spectrogram is carried out analytical calculation, promptly to horizontal ordinate X_{A left side}And X_RightBetween the ordinate value of spectrogram compare, find at horizontal ordinate X_{A left side}With 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 side}And 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 side}And 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 side}The position.L_{A left side}With L_RightParticular location neither be unique, L_{A left side}With 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 side}With L_RightBetween get final product.X_{A left side}And 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 side}And 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 side}And 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 side}With 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 side}And 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 hasKey, 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 i}Abscissa 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 i}Abscissa 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 i}Article 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 i}Article two, straight line;

Establishment analytical calculation subroutine, this program can be found out at straight line L_{Left side i}With straight line L_{Right i}Between 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 i}Article two, straight line carries out the picture composing, with the L of spectrogram and all localization_{Left side i}, L_{Right i}Article 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 onceKey is judged X_{Left side i}Whether less than MAX, if X_{Left side i}Less than MAX X then_{Left side i}Add 1 and deposit Addr in_{Left side i}In, repeating step (4) is to (6), otherwise repeating step (4) is to (6);

-whenever press onceKey judges whether i equals 1, if i equals 1, judges X_{Left side i}Whether greater than MIN, if X_{Left side i}Greater than MIN X then_{Left side i}Subtract 1 and deposit Addr in_{Left side i}In, repeating step (4) is to (6), otherwise repeating step (4) is to (6); If i is not equal to 1, judge X_{Left side i}Whether greater than X_{Right (i-1)}, if X_{Left side i}Greater than X_{Right (i-1)}, X then_{Left side i}Subtract 1 and deposit Addr in_{Left side i}In, repeating step (4) is to (6), otherwise repeating step (4) is to (6);

-as straight line L_{Left side i}When being transferred to the left margin of stripping signal peak of the tested element in the spectrogram, pressKey, X_{Left side i}Be identified, the flag value becomes " right side " by " left side ";

-whenever press once

Key is judged X_{Right i}Whether less than MAX, if X_{Right i}Less than MAX X then_{Right i}Add 1 and deposit Addr in_{Right i}In, repeating step (4) is to (6), otherwise repeating step (4) is to (6);

-whenever press onceKey is judged X_{Right i}Whether greater than X_{Left side i}, if X_{Right i}Greater than X_{Left side i}X then_{Right i}Subtract 1 and deposit Addr in_{Right i}In, repeating step (4) is to (6), otherwise repeating step (4) is to (6);

-as straight line L_{Right i}When being transferred to the right margin of stripping signal peak of the tested element in the spectrogram, pressKey, X_{Right i}Be identified, the flag value becomes " left side " by " right side ";

(7) judge X_{Right i}Whether greater than X_{A left side (i+i)}, if X_{Right i}Greater 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 N}And X_{Right (i+1)}, X_{Right (i+2)}... X_{Right N}All equal X_{Right i}, and deposit corresponding Addr in_{A left side (i+1)}, Addr_{A left side (i+2)}... Addr_{Left side N}And Addr_{Right (i+1)}, Addr_{Right (i+2)}... Addr_{Right N}In, connect step (8), otherwise:

(8) transfer the analytical calculation subroutine, the analytical calculation subroutine is from straight line L_{Left side i}With straight line L_{Right i}Between 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 y₁₁, Δ y₂₁... 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 i}With straight line L_{Right i}Between 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 y₁₂, Δ y₂₂... Δ y_N2Output;

(13) according to Δ y₁₁With Δ y₁₂, Δ y₂₁With Δ y₂₂... 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 i}And L_{Right i}Be respectively that horizontal ordinate equals X_{Left side i}And X_{Right i}Two straight lines, that is: L_{Left side i}Be X=X_{Left side i}, L_{Right i}Be X=X_{Right i}Straight line L_{Left side i}And L_{Right i}Just, adjust L in order to set the localization of analytical calculation_{Left side i}, L_{Right i}Sequencing unimportant, also can work out concrete computer program in actual applications, adjust earlier L_{Right i}The position, L is adjusted in the back_{Left side i}The position.X_{Left side i}And X_{Right i}Initial 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 i}And X_{Right i}Initial 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 i}Article two, straight line carries out the picture composing, forms the L of spectrogram and all localization_{Left side i}, L_{Right i}Article two, the reflection of the picture of straight line deposits among the BUFFER, then with L among the BUFFER_{Left side i}And L_{Right i}Article 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 side}And L_RightBetween localization after, generally do not need again boundary line L to localization_{A left side}And 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 side}With 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 reachedMake 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 side}With 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 i_{Left i}Abscissa value X_{Left 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 one_{Left i}、L_{Left i}And X_{Left i}Be respectively Addr_Left、L_LeftAnd X_Left；

Addr_{Right i}: boundary line, the right L that is used for depositing localization i_{Right i}Abscissa value X_{Right 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 one_{Right i}、L_{Right i}And X_{Right i}Be respectively Addr_Right、L_RightAnd X_Right；

Flag: sign, if it equals " left side ", L is being transferred in expression now_{Left i}If (when only establishing a measurement localization, be L_Left), if it equals " right side ", L is being transferred in expression now_{Right i}If (when only establishing a measurement localization, be L_Right). 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 side}Be 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 localization_{Left i}(or L_Left)、L_{Right i}(or L_Right) two straight lines carry out picture and set type, and form the L of spectrogram and all localization_{Left i}(or L_Left)、L_{Right i}(or L_Right) reflection of picture of two straight lines deposits among the BUFFER, then with L among the BUFFER_{Left i}(or L_Left) and L_{Right i}(or L_Right) 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 one_{Left i}(or L_Left)、L_{Right i}(or L_Right) two straight lines.

Establishment analytical calculation subprogram, this program can be to straight line L_{Left i}(or L_Left) and straight line L_{Right i}(or L_Right) between localization in the ordinate of spectrogram compare, find out maximum y wherein_maxWith minimum of a value y_min, and calculate Δ y=y_max-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 side}And L_RightHigh order end at lattice liquid crystal display screen LCD overlaps.

(4) read keyboard:

-whenever press onceKey is judged X_{A left side}Whether less than MAX.If X_{A left side}Less than MAX, X then_{A left side}Add 1 and deposit Addr in_{A left side}In, then judge X_RightWhether less than X_{A left side}, if X_RightLess than X_{A left side}, X then_Right=X_{A left side}Deposit 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 side}Be not less than MAX, repeating step (2) is to (4);

L in this process_{A left side}Adjusted L to the right_RightAlso follow L_{A left side}Adjusted to the right together.

-whenever press once

Key is judged X_{A left side}Whether greater than MIN, if X_{A left side}Greater than MIN, X then_{A left side}Subtract 1 and deposit Addr in_{A left side}In, repeating step (2) is to (4); Otherwise, if X_{A left side}Be not more than MIN, repeating step (2) is to (4);

In this process, L_{A left side}Adjusted left, be mainly used in and work as L_{A left side}Transfer to the right excessive after, use

Key is recalled to the origin-location with it again.

-as straight line L_{A left side}When being transferred to the left margin of strippingcurrent peak 1 of the Zn in the spectrogram, press

Key, X_{A left side}Be 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 side}Confirm, later on no longer change.

-whenever press onceKey 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 strippingcurrent peak 1 of the Zn in the spectrogram, pressKey, 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 side}And X_RightBetween the ordinate of spectrogram compare, find out X_{A left side}And 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 Zn₁=y_Max1-y_Min1, and deposit in the corresponding storage portions;

(6) by printer with Δ y₁Printout;

(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 side}With straight line L_RightBetween localization in spectrogram carry out analytical calculation, i.e. the X that step (4) is determined_{A left side}With X_RightBetween the ordinate of spectrogram compare, find out X_{A left side}And 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 Zn₂=y_Max2-y_Min2

(9) by printer with Δ y₂Printout;

(10) according to Δ y₁With 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 i}Article two, straight line carries out the picture composing, with the L of derivative spectrogram and all localization_{Left side i}, L_{Right i}Article 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 i}Article two, straight line;

At this moment, lattice liquid crystal display screen LCD goes up the derivative spectrogram that shows as shown in Figure 8, andpeak 1,2,3,4 is respectively the stripping current peak of Zn, Cd, Pb, Cu, straight line L in the derivative spectrogram_{Left side i}And L_{Right i}High order end at lattice liquid crystal display screen LCD overlaps.

(6) read keyboard:

---whenever press onceKey is judged X_{Left side i}Whether less than MAX, if less than MAX, X then_{A left side 1}Add 1 and deposit Addr in_{A left side 1}In, judge X_{A left side 1}Whether greater than X_{Right 1}, if X_{A left side 1}Greater than X_{Right 1}, X then_{Right 1}=X_{A left side 1}Deposit Addr in_{Right 1}In, if X_{A left side 1}Be not more than X_{Right 1}, then repeating step (4) is to (6); If X_{A left side 1}Be not less than MAX, then repeating step (4) is to (6);

-whenever press onceKey is judged: whether equal 1, if i equals 1 (equaling I this moment), judge X_{A left side 1}Whether greater than MIN, if X_{A left side 1}Greater than MIN, X then_{A left side 1}Subtract 1 and deposit Addr in_{A left side 1}In, repeating step (4) is to (6); If X_{A left side 1}Be not more than MIN, then repeating step (4) is to (6); If i is not equal to 1, judge X_{A left side 1}Whether greater than X_{Right (i-1)}, if X_{A left side 1}Greater than X_{Right (i-1)}, X then_{A left side 1}Equal X_{A left side 1}Subtract 1 and deposit Addr in_{A left side 1}In, repeating step (4) is to (6).If X_{A left side 1}Be not more than X_{Right (i-1)}, then repeating step (4) is to (6);

-as straight line L_{A left side 1}When being transferred to the left side at stripping electric currentderivative peak 1 of Zn in the derivative spectrogram, pressKey, X_{A left side 1}Be identified, the flag value becomes " right side " by " left side ";

-whenever press

Key is judged X_{Right 1}Whether less than MAX, if X_{Right 1}Less than MAX, X then_{Right 1}Add 1 and deposit Addr in_{Right 1}In, important step (4) is to (6), otherwise repeating step (4) is to (6);

-whenever press onceKey is judged X_{Right 1}Whether greater than X_{A left side 1}, if X_{Right 1}Greater than X_{A left side 1}, X then_{Right 1}Subtract 1 and deposit Addr in_{Right 1}In, repeating step (4) is to (6), otherwise repeating step (4) is to (6);

-as straight line L_{Right 1}When being transferred to the right side at stripping electric currentderivative peak 1 of the Zn in the derivative spectrogram, press

Key, X_{Right 1}Be identified, the flag value becomes " left side " by " right side ";

Determine L_{A left side 1}With L_{Right 1}Particular location the time, as long as can make by L_{A left side 1}With L_{Right 1}The summit of the posivtive spike at the stripping electric currentderivative 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 1}Whether greater than X_{A left side 2}, if X_{Right 1}Greater than X_{A left side 2}, the X oflocalization 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 4}All 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 4}In, connect step (8); If X_{Right 1}Be 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 1}With straight line L_{Right 1}Betweenlocalization 1 in the derivative spectrogram in, to X_{A left side 1}With X_{Right 1}Between 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 Zn₁₁=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 currentderivative peak 2,3,4 of Cd, Pb, Cu are provided withanalytical 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 y₂₁, Δ y₃₁, Δ y₄₁, by printer with Δ y₁₁, Δ y₂₁, Δ y₃₁, Δ y₄₁Printout;

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 4}As 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 1}With L_{Right 1}Between, L_{A left side 2}With L_{Right 2}Between, L_{A left side 3}With L_{Right 3}Between, L_{A left side 4}With L_{Right 4}Betweenlocalization 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, Cu₁₂=y_1max2-y_1min2, Δ y₂₂=y_2max2-y_2min2, Δ y₃₂=y_3max2-y_3min2, Δ y₄₂=y_4max2-y_4min2, and deposit in the corresponding storage portions;

(12) by printer with Δ y₁₂, Δ y₂₂, Δ y₃₂, Δ y₄₂Output;

(13) according to Δ y₁₁With Δ y₁₂, Δ y₂₁With Δ y₂₂, Δ y₃₁With Δ y₃₂, Δ y₄₁With Δ y₄₂And 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 side}Abscissa 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 side}With 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 onceKey is judged X_{A left side}Whether less than MAX, if X_{A left side}Less than MAX X then_{A left side}Add 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 side}Whether greater than MIN, if X_{A left side}Greater than MIN X then_{A left side}Subtract 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 side}When being transferred to the left margin of stripping signal peak of the tested element in the spectrogram, pressKey, X_{A left side}Be 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, pressKey, X_RightBe identified;

(5) transfer the analytical calculation subroutine, the analytical calculation subroutine is from straight line L_{A left side}With 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 element₁=y_Max1-y_Min1

(6) pass through the output device of computing machine with Δ y₁Output;

(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 side}With 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 y₂=y_Max2-y_Min2

(9) pass through the output device of computing machine with Δ y₂Output;

(10) according to Δ y₁With Δ y₂And 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 side}And 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 i}Abscissa 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 i}Abscissa 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 i}Article 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 i}Article two, straight line;

Establishment analytical calculation subroutine, this program can be found out at straight line L_{Left side i}With straight line L_{Right i}Between 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 i}Article two, straight line carries out the picture composing, with the L of spectrogram and all localization_{Left side i}, L_{Right i}Article 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 i}Article two, straight line;

(6) read keyboard:

-whenever press once

Key is judged X_{Left side i}Whether less than MAX, if X_{Left side i}Less than MAX X then_{Left side i}Add 1 and deposit Addr in_{Left side i}In, repeating step (4) is to (6), otherwise repeating step (4) is to (6);

-whenever press onceKey judges whether i equals 1, if i equals 1, judges X_{Left side i}Whether greater than MIN, if X_{Left side i}Greater than MIN X then_{Left side i}Subtract 1 and deposit Addr in_{Left side i}In, repeating step (4) is to (6), otherwise repeating step (4) is to (6); If i is not equal to 1, judge X_{Left side i}Whether greater than X_{Right (i-1)}, if X_{Left side i}Greater than X_{Right (i-1)}, X then_{Left side i}Subtract 1 and deposit Addr in_{Left side i}In, repeating step (4) is to (6), otherwise repeating step (4) is to (6);

-as straight line L_{Left side i}When being transferred to the left margin of stripping signal peak of the tested element in the spectrogram, press

Key, X_{Left side i}Be identified, the flag value becomes " right side " by " left side ";

-whenever press onceKey is judged X_{Right i}Whether less than MAX, if X_{Right i}Less than MAX X then_{Right i}Add 1 and deposit Addr in_{Right i}In, repeating step (4) is to (6), otherwise repeating step (4) is to (6);

-whenever press once

Key is judged X_{Right i}Whether greater than X_{Left side i}, if X_{Right i}Greater than X_{Left side i}X then_{Right i}Subtract 1 and deposit Addr in_{Right i}In, repeating step (4) is to (6), otherwise repeating step (4) is to (6);

-as straight line L_{Right i}When being transferred to the right margin of stripping signal peak of the tested element in the spectrogram, press

Key, X_{Right i}Be identified, the flag value becomes " left side " by " right side ";

(7) judge X_{Right i}Whether greater than X_{A left side (i+1)}, if X_{Right i}Greater 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 N}And X_{Right (i+1)}, X_{Right (i+2)}... X_{Right N}All equal X_{Right i}, and deposit corresponding Addr in_{A left side (i+1)}, Addr_{A left side (i+2)}... Addr_{Left side N}And Addr_{Right (i+1)}, Addr_{Right (i+2)}... Addr_{Right N}In, connect step (8), otherwise:

(8) transfer the analytical calculation subroutine, the analytical calculation subroutine is from straight line L_{Left side i}With straight line L_{Right i}Between 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 y₁₁, Δ y₂₁... 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 i}With straight line L_{Right i}Between 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 y₁₂, Δ y₂₂... Δ y_N2Output;

(13) according to Δ y₁₁With Δ y₁₂, Δ y₂₁With Δ y₂₂... 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 i}Article two, straight line carries out the picture composing, forms the L of spectrogram and all localization_{Left side i}, L_{Right i}Article two, the reflection of the picture of straight line deposits among the BUFFER, then with L among the BUFFER_{Left side i}And L_{Right i}Article two, the picture color negate between the straight line, promptly be originally " bright " point become " secretly " point, be originally put " secretly " become " bright " point.

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