JPS63314447A - Solution circulation type automatic absorption spectrochemical analysis - Google Patents

Abstract

PURPOSE:To enable reduction in a required analysis time while achieving a higher accuracy of an automatic spectrochemical analysis, by a method wherein calibration curves of absorbance and the amount of ions are set on an arithmetic unit beforehand and a mean of measured values obtained by measuring absorbance several times each in color ion colora tion and color formation areas is introduced into the arithmetic unit to determine the amount of ion from the calibration curves. CONSTITUTION:A sample solution is introduced into a reaction tank 2 from a sample solution tank 1 while a sample is introduced into the tank 2 from reagent tanks 3a-3e to reduce Fe<3+> to Fe<2+>. Thereafter, light is emitted from a light emitting body 7 moving a sample solution to a flow cell 6 to measure absorbance several times in a color ion coloration area with a photoelectric multiplier tube 8 and a mean thereof is computed and introduced into an arithmetic unit 9 on which reference calibration curves of absorbance and the amount of ion are previously set. Then, color forming reagents from the tanks 3a-3e are introduced to the tank 2 to make a color forming ion. Likewise, absorbance in an emission area is measured several times moving the color forming ion to the flow cell 6 to compute a mean. The results are introduced to the arithmetic unit 9 to perform a computation combining the results of measurement in a color ion coloration area and the amount of ion is analyzed from the calibration curves set to display 10.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a solution circulation type automatic absorption analysis method.

(Prior art) A solution circulation type automatic absorption spectrometry method is widely known as an analysis method for P, Mn, ■, A1, etc.; As disclosed, even though the measurement itself is done automatically, the absorbance is measured once in the colored ion coloring region and once in the coloring region, so errors sometimes occur and analytical values become inaccurate. Sometimes. Furthermore, analysis after measurement is mainly done manually, resulting in disadvantages such as a lack of speed.

(Problems to be Solved by the Invention) The problem to be solved by the present invention is to eliminate the above-mentioned drawbacks, improve the accuracy of automatic light exposure analysis, and shorten the time required for analysis.

(Means for solving problems) What about the present invention? In the 8-liquid circulation automatic absorption analysis method, a calibration curve of absorbance and ion amount is set in advance on the computer, and the absorbance is measured multiple times in the colored ion coloring region and coloring region.
The method is characterized in that the average value of each measured value is sent to the medical calculator and the amount of ions is determined from the calibration curve.

In the present invention, first, the relationship between absorbance and ion amount is set in advance as a standard calibration curve in the calculator, and during actual measurement, the absorbance is measured multiple times each in the colored ion coloring region and the coloring region. . In other words, in the past, only one measurement was taken in each of these regions, and it became clear that this was a contributing factor to inaccurate analysis results. Each measurement is performed multiple times, and the average value of each measurement value is used as the standard.Also, to avoid time loss caused by repeating absorbance measurements multiple times, it is necessary to calculate the absorbance and ion content in advance for the analysis to be performed after the measurement. This problem was solved by speeding up the calculation by calculating the relationship between the two using a calculator that had been set as a standard calibration curve. In other words, in the colored ion coloring region, for example, in the analysis of impurities in steel, a reduction action of Fe"-+Fe" is performed, stirring with the coloring solution, air removal, etc., resulting in abnormal values in the measurement. Therefore, in the present invention, the absorbance is measured multiple times in this colored ion coloring region as described above, and the values excluding abnormal values are averaged. In addition, in the coloring region, the luminescence solution and sample solution are stirred, and abnormal values appear in the measurement as in the case of absorbance measurement in the colored ion coloring region, so the absorbance is measured multiple times in this coloring region. The average value is sent to a computer along with the measured average value of the colored ion color range and compared with a calibration curve, thereby determining the amount of ions. Because the process is carried out in the process, analysis based on the measurement results can be carried out extremely quickly, and the time loss caused by measuring the absorbance multiple times can be compensated for. Note that the more times the absorbance is measured, the more accurate the analysis can be, but considering the measurement time etc., it is appropriate to measure absorbance once per second x 5 times.
In addition to Mn, V, and AlSMn, it can be effectively applied to various analyzes using conventional absorbance analysis methods.

Next, an example of the method of the present invention will be explained with reference to the drawings.
In the figure, +11 is the sample solution tank, (2) is the reaction tank, (3
a), (3b), (3c), (3d), and (3e) are all reagent tanks. Now, while introducing the sample solution from the sample solution tank (11) into the reaction tank (2), the reagent tanks (3a) and (3
The reagents from b), (3c), (3d), and (3e) are led to the reaction tank (2), and while being heated with the heater (4), Fe'' is
After being reduced to e''+, the sample solution (colored ions) is circulated to the flow cell (6) by air blowing from the air blowing tube (5), and - the luminescent material (7) is injected into the flow cell (6).
), the absorbance of one color ion color range is measured multiple times using Photomar (8), the average value is calculated, and the results are calculated by setting a standard calibration curve of absorbance and ion amount in advance. Introduce into container (9). Next, a reagent tank (3a),
The coloring reagents from (3b), (3C), (3d), and (3e) are led to the reaction tank (2) to form coloring ions, which are circulated and transferred to the flow cell (6) in the same manner as above, and the luminescent material (7)
The absorbance of the luminescent region is measured multiple times using a photomultiplier (8), the average value is calculated, and the result is led to the arithmetic unit (9) and combined with the measurement results of the colored ion color region. The amount of ions is analyzed from a calibration curve that is preset in this calculator (9), and the results are sent to the printer α.
Display to.

(Example) Next, examples of the present invention will be listed together with comparative examples.

(Example of analysis of P in tiA) 0.1 g of cut steel sample was treated with 5 cc of nitric acid and perchloric acid (60 cc).
%), heat and dissolve, and treat with white smoke to reduce the remaining amount of perchloric acid to 1 cc or less. After adding water to this to dissolve the salts, the total volume is adjusted to exactly 25 cc and this is used as a sample solution. Next, the above sample solution was transferred to a reaction tank, 10 cc of sodium bisulfite solution (20%) was added, and F
Fe3+! After reducing to +, the absorbance of colored ions such as nickel and chromium was measured 5 times at a measurement interval of 1 time/second, and the absorbance (A) at this time was 0.007.
It was 0.007.0, OO6, 0,010, 0,007.

Next, ammonium molybdate (2
, 5%) 10cc and hydrazine sulfate solution (3%) 14
cc was added and after the color development was completed, the absorbance was measured 5 times at a measurement interval of 1 time/second, and the absorbance (B) at this time was o, o s o, o, o s o, 0.058, O
,,051,0,055. By the way, in general, in solution circulation type automatic absorption analysis, a method is used in which the solution is circulated between the reaction tank and the absorbance measurement cell by aeration.
At this time, an abnormal value may be shown at a frequency of about 3/25 times due to the inclusion of air bubbles, but the abnormal value is always a high abnormal value due to scattering by air bubbles, so the above five measured values are After arranging the absorbance in descending order of absorbance, remove the two highest measured values, calculate the average value of the three lowest measured values, and calculate the value (corrected A calibration curve as shown in FIG. 2 was set in advance, and the absorbance was introduced into a calculator and determined to be P-19.5 μg/g.

(Comparative example) Absorbance (A) = O1007, which is the measured value obtained by measuring the absorbance once in the colored ion coloring region under the same conditions as in the above example, and Absorbance (B), which is the measured value obtained by measuring the absorbance once in the colored ion region -0,050 was calculated using the above formula, and this value was determined to be P = 19.3 μg/g from a predetermined calibration curve.

As a result of analyzing P in the same steel 10 times in each of the examples and comparative examples, as shown in the table below, the analysis according to the present invention had little variation and was able to improve accuracy.

(Effects of the Invention) As is clear from the above description, the present invention uses absorbance measurements in the colored ion coloring region and the coloring region as average values of multiple measurements, while the analysis after measurement is performed using the absorbance in advance. By setting a calibration curve for the amount of ions and ions and performing the analysis using an i* calculator, we were able to improve the accuracy of the analysis, make automatic analysis applicable to the extremely trace amount range, and shorten the time required for a series of analyses. This method will greatly contribute to the development of the industry as it solves the problems of the conventional solution circulation type automatic absorption analysis method.

[Brief explanation of drawings]

FIG. 1 is an explanatory diagram showing an example of an apparatus for carrying out the method of the present invention, and FIG. 2 is a graph showing the timing of measuring absorbance. Patent Applicant Nippon Steel Corporation Nippon Steel Combita System Co., Ltd. Representative Fujiwara Seisakusho Co., Ltd. Person Name Akira Shima Immediate Question Tatsu Watanuki
Rimayama main text
husband figure 1

Claims (1)

[Claims] A calibration curve of absorbance and ion amount is set in the calculator in advance, and the absorbance is measured multiple times in the colored ion coloring region and the coloring region, respectively, and the average value of each measurement value is led to the calculator to create the calibration curve. A solution circulation type automatic absorption analysis method characterized by determining the amount of ions from.