JPS59157538A - Analyzer applicable with standard adding method - Google Patents

Abstract

PURPOSE:To generate a calibration line without moving the lateral axis nor longitudinal axis of a graph on a screen on every measurement by inverting the extrapolation part of the calibration line and displaying the extrapolation part on a screen within the same quadrant as the quadrant wherein a measured value is displayed. CONSTITUTION:The measured value from a sample measurement part 10 and a density value from a console panel 11 are inputted from input terminals 1 and 2 and stored in a storage part 3. When data on a sample with largest standard added amount which is measured firstly is established, a coordinate axis and scale generation part 4 generates coordinate axes and scales on the basis of the data, and sends coordinate axis display data 41 to a display part 6 to display the data together with the current plotting data 31. Then, each measurement point is plotted on the screen every time a sample to which standard material of the same kind with a component to be calibrate is added is measured, and when the final data is established, all data are sent to a calibration line generation part 5 to generate the mean line of all points. The calibration line is worked by an inversion composition part 7 so that the part in the 2nd quadrant is folded into the 1st quadrant, and then displayed while superposed upon the plotting data on the display part 6.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to an analyzer to which a standard addition method can be applied, and more particularly to an analyzer equipped with a display section for graphically displaying a calibration curve.

[Background of the invention]

The standard addition method is known as an effective quantitative method when the composition of the sample is unclear, it is difficult to remove the effects of chemical or physical interference during measurement, and accurate quantification cannot be achieved using the normal calibration curve method. ing.

This method is also effective when used as an indirect measurement when the amount of material contained in the sample is so small as to be at the limit of measurement, and the S/N ratio is too small for direct measurement to be accurate.

′ To explain the procedure for quantification using the standard addition method, standard substance solutions of different concentrations are added to multiple analytical samples divided into equal volumes, each solution is measured, and the horizontal axis shows the added standard substance solution. Plot the data for each sample on graph paper with measured values (e.g., absorbance) on the vertical axis, and draw a straight line that passes through those points on average. This state is shown in Figure 1, where points A, B,
C.

D is the measurement point, and the distance between the origin and the point where a straight line t drawn to pass through these points on average intersects with the horizontal axis is x(1). This will be read as a negative value, but this will be replaced with a positive value to determine the concentration of the sample.Also, when using it as an indirect measurement, do not measure point A, which has low reliability, but measure points B, C,
Extrapolate from D to read point A and concentration XQ.

This method has the trouble of having to plot points on a graph and draw a straight line for each sample, and is also prone to errors when plotting data points, drawing straight lines, and reading distances. The major drawback is that the reliability of the results cannot be higher than a certain level due to individual differences. Furthermore, depending on how you choose the scale of the graph, the position of the plotted point and concentration x,) may change, resulting in decreased accuracy, or it may be necessary to redraw the graph because it extends beyond the page. .

The calibration curve display device shown in FIG. 2 is an improvement over these shortcomings, and is composed of a microcomputer storage, an arithmetic section, and a CR'r display section.

The procedure for quantitative analysis in Maki 2 diagram will be explained. First, each prepared sample is measured in turn with the analyzer 10, and the results are sent to the storage unit 3 from the measured value input terminal 1 connected online, and the standard substance is sent to the concentration value input terminal 2 by means such as numerical keys. , and the mutual input values are stored in the storage unit 3 as a pair of data. This is repeated until all the samples have been measured, and upon completion of the measurement, the data in the storage section 3 is sent to the calibration curve creation section 5 and the coordinate axis scale creation section 4 to determine the calibration curve, coordinate axis positions, and scale values, respectively. The images are synthesized and displayed on the display unit 6. The display screen at this time will be as shown in FIG.

Although this method saves the analyst the trouble of plotting on graph paper and drawing straight lines, and solves the problems of calculation accuracy and individual differences, the following drawbacks remain. In other words, the scales for the vertical and horizontal axes cannot be determined and graphed until after all samples have been measured, so even if abnormal data is included during the measurement, all samples will not be measured. It cannot be discovered until it is graphed. Furthermore, since the position of the coordinate axes on the screen is determined according to the measurement data, the position of the vertical axis changes with each measurement, making it difficult to see.

[Purpose of the invention]

An object of the present invention is to provide an analyzer that can apply the standard addition method and can graphically display the component concentration of an unknown sample within the same quadrant in which the measured values are plotted.

[Summary of the invention]

The present invention displays the extrapolated portion on the screen in the same quadrant in which the measured values are displayed by inverting the extrapolated portion of the calibration curve calculated by measuring multiple samples to which standard substances have been added. It is characterized by

[Embodiments of the invention]

According to a preferred embodiment of the present invention, graphing is possible within the initially set scale (vertical and horizontal axes), so the measurement points are plotted on the display screen of a CRTfi for each measurement of each sample. can. Therefore, it is easy to discover abnormal data during the process, and the screen space can be used effectively.

It is desirable in the present invention to select only the first quadrant of the calibration curve graph as the effective display range, and to display the second quadrant at the same time on the display screen of the first quadrant by folding the second quadrant from the coordinate axis. By doing this, the coordinate axes can be drawn before the contents of the second quadrant are determined, and the scale on the screen can be determined at the time when the sample with the highest additive amount is measured. Then, each measurement point can be plotted on the screen each time a sample is measured thereafter, and the measurement work can be carried out efficiently.

The completed calibration curve does not have overlapping parts due to folding of the screen, and the position indicating the desired concentration value can be read as a positive value on the coordinate axes, so reading errors are less likely to occur. Also,
1st. ．． Compared to the traditional method of displaying both quadrants,
The display resolution of plotted points becomes higher.

Embodiments of the present invention will be described in detail below with reference to the drawings.

FIG. 3 is a diagram showing an embodiment of the present invention. The atomic absorption spectrophotometer receives the measured values from the sample measuring section 10 and the concentration values from the numerical keys on the operation panel 11 through the input terminals 1 and 2.
, and is stored in the storage unit 3. When the data of the sample to be measured first with the highest addition amount of standard substance is established, the coordinate axes and scales are created in the coordinate axes/scale creation section 4 based on this data, and as a result, the coordinate axes display data 41 are CR, T
The plot data 3 at that time is sent to the display section 6 consisting of
Displayed together with 1. After that, each measurement point is plotted on the screen each time a sample containing the same type of standard substance as the test component is measured, and when the final data is established, all data is transferred to the calibration curve creation section 5. to create a straight line that passes through all points on average.

The calibration curve is processed by the inversion synthesis section 7 into a shape in which the second quadrant is folded back into the first quadrant, and is displayed superimposed on the data already plotted on the display section 6. The calibration curve 71 created by the inversion synthesis section 7 at this time is given by equation (2) when the equation of the original calibration curve is defined as equation (1).

x=ay+b...(1)x=
l a y + b l - (2) where X is the concentration, y is the measured value, and a and b are coefficients.

FIG. 4 is an example of a screen created in this way. As is clear from FIG. 4, in order for the XoO value to be read within the range of this screen, the measured value at point A must be below the halfway position on the vertical axis.

This is necessary to maintain the accuracy of XQ determined by extrapolation, and also coincides with the conditions in the general standard addition method. If point A is located above the vertical axis and XQ protrudes from this screen, the scale will be corrected and plotted again, making it easier to re-prepare the sample with an increased amount of the standard substance added to make the measurement easier. fix. As described above, according to this example, in addition to having the above-mentioned characteristics, the calibration curve for the standard addition method can be used to judge the appropriateness of the addition amount during the measurement, and can avoid unnecessary measurements. Can be displayed.

FIG. 5 is a diagram showing the operational flow of an embodiment in which a calibration curve is created using a microcomputer.

〔Effect of the invention〕

As can be understood from the above explanation, according to the present invention, the component concentration of an unknown sample can be displayed graphically in the same quadrant in which the measured values of the sample to which the standard substance has been added are plotted on the screen. It is possible to create a calibration curve for the standard addition method without having to move the horizontal or vertical axes of the graph in screen 2 each time.

[Brief explanation of drawings]

Figure 1 is a diagram for explaining the conventional standard addition method, Figure 2 is a diagram that would be expected when the method in Figure 1 is executed on a CRT screen, and Figure 3 is an illustration of an embodiment of the present invention. FIG. 4 is an explanatory diagram showing an example of a calibration curve displayed on a CRT screen according to the embodiment, and FIG. 5 is an operation flowchart for displaying a calibration curve on the screen. 3...Storage unit, 4...Coordinate axis/scale creation unit, 5...
- Calibration curve creation section, 6...Display section, 7...Inversion synthesis section, 1o...Sample measurement section, Xo...I from the intersection on the horizontal axis to the origin Figure 12 Figure 5 J Figure 4 Figure 4 '45 Figure A A Tin input water E Ingredients 5 traces on concentration check L; A f=51/L/l'
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Claims (1)

[Claims] 1. A sample measurement section, a calculation section that calculates a calibration curve based on the measured values of the test components of the sample from this sample measurement section, and a graph on the screen that shows the relationship between the concentration value and multiple measured values as a calibration curve. In an analyzer capable of applying the standard addition method, which is equipped with a display section that displays, the extrapolated portion of the calibration curve is inverted so that the extrapolated portion is displayed in the same quadrant as the measured value is displayed. An analyzer to which a standard addition method can be applied, characterized in that a means for inputting a signal to the display section is provided.