KR0158562B1 - Fluorescent x-ray analysis method of micro-chlorine ion using paper disc method - Google Patents

Fluorescent x-ray analysis method of micro-chlorine ion using paper disc method Download PDF

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KR0158562B1
KR0158562B1 KR1019940040298A KR19940040298A KR0158562B1 KR 0158562 B1 KR0158562 B1 KR 0158562B1 KR 1019940040298 A KR1019940040298 A KR 1019940040298A KR 19940040298 A KR19940040298 A KR 19940040298A KR 0158562 B1 KR0158562 B1 KR 0158562B1
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aglα
solution
clkα
intensity
chlorine ion
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KR960024345A (en
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소재춘
김정호
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김만제
포항종합제철주식회사
신창식
재단법인산업과학기술연구소
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    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
    • G01N23/223—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material by irradiating the sample with X-rays or gamma-rays and by measuring X-ray fluorescence

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Abstract

여지법을 이용한 용액 중 미량 염소이온 형광 X-선 분석방법에 있어서, ClKα와 AgLα강도를 동시에 측정하여 AgLα의 강도를 내부표준으로 사용하여 표준용액을 이용하여 염소이온의 농도 대 ClKα/AgLα 강도와의 검량곡선을 작성 한 후, 분석하고자 하는 시료용액의 ClKα/AgLα을 측정한 후 앞서 작성된 검량곡선을 이용하여 염소이온을 정량분석한다.In the trace chlorine ion fluorescence X-ray analysis method using the excitation method, the ClKα and AgLα intensities were measured simultaneously, and the concentration of chlorine ion versus ClKα / AgLα intensity After preparing the calibration curve of, measure the ClKα / AgLα of the sample solution to be analyzed and quantitatively analyze the chlorine ions using the previously prepared calibration curve.

Description

여지법을 이용한 용액 중의 미량 염소이온 형광 X-선 분석방법Trace Chloride Fluorescence X-ray Analysis in Solution Using Filter Method

제1도는 기존의 여지법에 의한 시료조제과정을 나타낸 공정도.1 is a process chart showing a sample preparation process according to the existing filter method.

제2도는 기존의 분석방법에 의해 작성된 검량곡선.2 is a calibration curve prepared by the existing analysis method.

제3도는 본 발명에 의한 분석방법에 의해 작성된 검량곡선.3 is a calibration curve created by the analysis method according to the present invention.

본 발명은 용액 중의 염소이온 형광 X-선 분석방법에 관한 것이며, 보다 상세히는 액체시료를 분석할 때 널리 사용되고 있는 여지법을 이용한 시료조제과정을 거쳐 용액 중에 미량 함유되어 있는 염소이온의 농도를 보다 정확히 정량분석 할 수 있도록 한, 용액 중 미량 함유되어 있는 염소이온에 대한 형광 X-선 분석법에 관한 것이다.The present invention relates to a chlorine ion fluorescence X-ray analysis method in a solution, and more particularly to the concentration of the chlorine ions contained in the solution through a sample preparation process using a method widely used when analyzing liquid samples The present invention relates to fluorescence X-ray spectroscopy for trace amounts of chlorine ions in solution.

일반적으로 형광 X-선 분석법에 사용되는 액체시료에 대한 시료조제 방법으로는 용액 상태의 시료를 액체시료 용기에 넣고 분석하는 용기법과, 제1도에 도시된 바와 같이 여과지(1)에 스탬프(2)를 이용하여 일정 크기의 원형띠(3) 모양으로 파라핀을 발라준 후 마이크로피펫(4)을 사용하여 시료용액(5)을 파라핀 원형띠(3) 안쪽에 일정량 적하하고 시료용액을 건조시킨 후 시료용기(6)의 크기에 맞게 이를 절단하여 분석을 실시하는 여지법 등이 사용되고 있다.In general, a sample preparation method for a liquid sample used in fluorescence X-ray analysis includes a container method in which a sample in a solution state is placed in a liquid sample container and analyzed, and a stamp (2) on a filter paper (1) as shown in FIG. After applying paraffin in the shape of a circular band (3) of a certain size, use a micropipette (4) to drop a certain amount of the sample solution (5) into the inside of the paraffin circular band (3), and then dry the sample solution. A room method for cutting the sample container 6 and analyzing it according to the size of the sample container 6 is used.

그러나, 액체시료 용기를 사용하는 용기법의 경우, 용기에 시료를 주입하는 것이 불편할 뿐만 아니라 시료주입량을 적게 하면 용기 내부에 기포가 형성되어 분석 오차가 발생할 우려가 있으며, 이를 방지하기 위하여 시료 주입량을 많이 하면 시료용액이 넘쳐흘러 산용액에 의해 금속제 시료용기가 부식되거나 피부를 상하게 하는 문제점들을 갖고 있어 도금액을 비롯한 많은 액체시료들을 분석할 때는 주로 여지법에 의한 시료조제방법이 널리 이용되고 있다.However, in the case of a container method using a liquid sample container, not only is it inconvenient to inject a sample into the container but also a small amount of sample injection may cause bubbles to form inside the container, which may cause an analytical error. In many cases, the sample solution overflows and the metal sample container is corroded by the acid solution or the skin is damaged. Thus, when analyzing many liquid samples including the plating solution, the sample preparation method mainly by the excitation method is widely used.

하지만 여지법을 사용하여 염소이온과 같이 휘발성이 강한 원소를 정량분석할 경우에는 여과지 위에 시료용액을 잠적한 후 건조시키는 과정에서 염소이온 중의 일부가 휘발되어 날아가 버려 분석이 불가능하게 되는 문제점이 있었다.However, when quantitative analysis of highly volatile elements such as chlorine ions using the excitation method, there was a problem that some of the chlorine ions are volatilized and fly away in the process of dripping the sample solution on the filter paper and drying it, making it impossible to analyze.

따라서, 최근에 본 발명자는 이러한 문제점을 해결하기 위하여 건조과정에서 염소이온이 휘발되는 것을 방지해 주는 새로운 점적여지를 개발하여 특허출원한 바 있다(한국특허출원 93-31672). 이에 의하면 시료용액을 점적여지에 적하하기 전에 미리 점적여지 중앙에 일정량(30㎕가 이상적임)의 AgNO3용액을 적하한 후 건조시켜 사용토록 함으로서 시료용액이 약품처리된 점적여지에 점적되었을 때 시료용액 중에 함유되어 있는 염소이온들을 미리 점적·건조시켜 놓은 AgNO3와 반응시켜 안정한 AgCl로 변화시켜 주어 건조과정에서 휘발되는 것을 방지토록 한 다음, 형광 X-선 분석기로 ClKα 선의 강도를 측정하여 정량분석 하도록 한 방법으로서 현재 제철소 등에서 널리 사용되고 있다.Therefore, in order to solve such a problem, the present inventors have recently developed and applied for a patent for a new drop margin for preventing volatilization of chlorine ions during the drying process (Korean Patent Application 93-31672). According to this, a certain amount of AgNO 3 solution (30 µl is ideal) was added dropwise to the center of the dropping solution before drying before dropping the sample solution, and then dried and used. Chlorine ions contained in the solution are reacted with AgNO 3 previously dipped and dried to convert into stable AgCl to prevent volatilization during drying, and then quantitatively analyzed by measuring the intensity of ClKα rays with a fluorescent X-ray analyzer. As a method to be used, it is widely used in steel mills and the like now.

그러나, 이 방법은 시료조제과정에서 염소이온이 휘발되는 것을 방지할 수 있게 하는데는 탁월한 능력을 발휘하였으나, 점적여지 위에 AgNO3용액 30㎕를 정확히 점적하는 작업이 어려워, 점적여지 위에 AgNO3용액을 점적하는 과정에서 점적량이 조금씩 변화하게 되었으며, 그 결과로서 형광 X-선 분석기로 ClKα 선의 강도를 측정하여 정량분석하는 과정에서 AgNO3에 의한 공존원소의 영향을 크게 받아 분석오차가 상대적으로 커지는 문제점이 발생되었다. 따라서 이러한 분석 방법을 분석 오차가 상대적으로 커도 괜찮은 공정분석 등에 적용하는 데는 아무런 문제가 없으나 보다 정밀한 분석이 요구되는 시료용액의 경우에는 이러한 방법을 이용하여 분석하는 것은 그 결과의 신뢰도에 문제가 있는 것이다.This method, however, the AgNO 3 solution over a difficult task to accurately drip the AgNO 3 solution 30㎕, exclusive room can be above, but exhibit a superior ability, exclusive room to allow to prevent the chlorine ions volatilized from the sample preparation process, During the dripping process, the dripping amount changed little by little, and as a result, the measurement error was largely affected by the coexistence element of AgNO 3 in the process of quantitative analysis by measuring the intensity of ClKα ray with the fluorescent X-ray analyzer. Occurred. Therefore, there is no problem in applying such an analytical method to a process analysis that may have a relatively large analysis error. However, in the case of a sample solution requiring more precise analysis, the analysis using this method has a problem in the reliability of the result. .

이에 본 발명의 목적은 상기와 같은 종래의 문제점을 해결한 보다 개선된 용액 중 미량 염소이온 형광 X-선 분석방법을 제공하는 것이다.Accordingly, an object of the present invention is to provide a trace chlorine ion fluorescence X-ray analysis method in a more improved solution that solves the above conventional problems.

본 발명에 의한 분석방법은 시료조제시 염소이온이 휘발되는 것을 방지하기 위해 시료용액중에 함유되어 있는 염소이온을 질산은(AgNO3)와 반응시킨 다음 형광 X-선 분석기로 시료 중에 함유된 염소이온 함량을 분석하는, 여지법을 이용한 용액 중의 미량 염소이온 형광 X-선 분석방법에 있어서, ClKα와 AgLα의 강도를 동시에 측정하여 AgLα의 강도를 내부표준으로 사용하여 표준용액을 이용하여 염소이온의 농도 대 ClKα/AgLα 강도비와의 검량곡선을 작성 한 후, 분석하고자 하는 시료용액도 동일한 방법으로 시료 조제를 한 후 ClKα/AgLα의 강도를 측정하고 앞서 작성된 검량곡선을 이용하여 정량분석을 실시함을 특징으로 한다.The analytical method according to the present invention reacts chlorine ions contained in the sample solution with silver nitrate (AgNO 3 ) in order to prevent volatilization of chlorine ions during sample preparation, and then chlorine ion content contained in the sample by a fluorescent X-ray analyzer. In the trace chlorine ion fluorescence X-ray analysis method using the excitation method, the intensity of ClKα and AgLα are simultaneously measured and the intensity of AgLα is used as an internal standard. After preparing the calibration curve with the ClKα / AgLα intensity ratio, the sample solution to be analyzed is prepared in the same way, and then the intensity of ClKα / AgLα is measured and quantitative analysis is performed using the calibration curve previously prepared. It is done.

이하, 본 발명에 대하여 상세히 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

본 발명에서는 기존의 시료조제방법과 동일한 방법으로 시료를 조제한 후 형광 X-선 분석기를 이용하여 정량분석을 실시할 때, 기존의 분석방법에서는 ClKα선의 강도만을 측정하여 정량분석 하였으나, 본 발명에 의한 분석방법에서는 ClKα 뿐만 아니라 AgLα의 강도를 동시에 측정하여 AgLα의 강도로부터 점적여지 위에 적하된 AgNO3용액 점적량의 변화량을 감지할 수 있을 뿐만 아니라 ClKα선을 내부 표준으로 사용하여 표준용액을 이용하여 염소이온의 농도대 ClKα/AgLα 강도와의 검량곡선을 작성한 후 분석하고자 하는 미지 시료용액의 경우도 동일한 방법으로 시료조제를 한 후 ClKα/AgLα 강도를 측정하여, 상기 검량곡선을 이용하여 정량분석을 실시한 결과 표준편차값이 0.0048 중량%인 매우 양호한 분석 결과를 얻을 수 있는 것이다.In the present invention, when the sample was prepared in the same manner as the conventional sample preparation method and then quantitative analysis using a fluorescence X-ray analyzer, in the conventional analytical method, only the intensity of ClKα ray was measured and quantitatively analyzed. In the analysis method, the intensity of AgLα as well as ClKα can be measured at the same time to detect the change in the amount of AgNO 3 solution dropped from the AgLα intensity onto the drip filter. After preparing a calibration curve with the concentration of ions versus ClKα / AgLα intensity, the unknown sample solution to be analyzed was prepared in the same manner, and then the ClKα / AgLα intensity was measured and quantitative analysis was performed using the calibration curve. Results Very good analytical results with a standard deviation of 0.0048% by weight can be obtained.

이하, 본 발명을 실시예를 통해 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail with reference to Examples.

[실시예]EXAMPLE

여지법을 이용하여 형광 X-선 분석법으로 용액 중에 함유되어 있는 염소이온의 함량을 정량분석하기 위하여 먼저 2.OM AgNO3용액을 조제한 후 점적여과지 위에 30㎕를 적하하고 건조기로 45-50℃의 온도로 온풍건조시켜 여러 개의 점적여과지를 제조하였다. 그 후 시판되고 있는 염산용액을 구입하여 Cl의 함량이 0-0.6중량%가 되도록 하기 표 1에서와 같은 농도를 갖는 표준용액 10개를 조제하여 사용하였다.In order to quantify the content of chlorine ions contained in the solution by fluorescence X-ray spectroscopy, a solution of 2.OM AgNO 3 was first prepared, and 30 μl was added dropwise onto a drop filter paper, and then dried at 45-50 ° C. with a drier. Several drop filters were prepared by drying with warm air. Thereafter, a commercial hydrochloric acid solution was purchased, and 10 standard solutions having a concentration as shown in Table 1 were used so that the Cl content was 0-0.6% by weight.

표준용액의 조제를 완료한 후, 약품처리를 한 점적여과지에 표준용액 30㎕를 적하하고 건조기로 열풍 건조시킨 후 형광 X-선 분석기로 기존의 분석방법인 ClKα의 강도를 측정하여 검량곡선을 작성하였으며, 그 결과를 제2도에 나타내었다.After preparing the standard solution, add 30 µl of the standard solution to the chemically treated drop filter paper, dry it with hot air, and measure the intensity of ClKα, a conventional analytical method, using a fluorescent X-ray analyzer. The results are shown in FIG.

동일한 표준시료들을 이용하여 이번에는 본 발명에 의한 ClKα/AgLα의 강도비를 측정하여 검량선을 작성하였는데, 그 결과는 다음의 제3도에 나타내었다.Using the same standard samples, a calibration curve was prepared by measuring the intensity ratio of ClKα / AgLα according to the present invention, and the results are shown in FIG.

검량곡선 작성 결과, 기존의 분석방법에 의한 검량곡선의 정확도는 0.027중량% 이었으며, 본 발명에 의한 검량선의 정확도는 0.063중량%로 나타났다.As a result of preparing the calibration curve, the accuracy of the calibration curve according to the existing analysis method was 0.027% by weight, and the accuracy of the calibration curve according to the present invention was 0.063% by weight.

검량곡선의 작성을 완료한 후, 미지 시료용액을 동일한 방법으로 시료조제를 한 다음 기존의 방법으로 정량분석을 실시하여 얻은 분석결과와, 다시 본 발명을 이용하여 동일한 시료에 대해 정량분석하여 얻은 분석결과를 서로 비교하여 나타내었는데 그 결과는 하기 표 2와 같았다.After completing the calibration curve, the sample obtained by preparing the unknown sample solution in the same way and then quantitatively analyzed by the existing method, and again the quantitative analysis of the same sample using the present invention The results were compared with each other and the results are shown in Table 2 below.

이와 같은 실험을 수행한 결과, 기존의 분석방법을 이용하여 분석한 분석결과의 정확도는 0.035중량%로 나타났으며, 그와 반대로 본 발명을 이용하여 분석한 분석결과의 정확도는 0.0048중량%로서 매우 양호한 분석결과를 얻을 수 있었다.As a result of the experiment, the accuracy of the analysis results analyzed using the existing analysis method was found to be 0.035% by weight, on the contrary, the accuracy of the analysis results analyzed using the present invention was 0.0048% by weight. Good analysis results were obtained.

실시예에 나타난 바와 같이, 여지법을 이용하여 시료조제를 한 후 형광 X-선 분석법으로 용액중 미량 함유되어 있는 염소이온의 함량을 정량분석 할 경우에는 본 발명에 의한 분석방법을 사용하여 분석을 실시하면 매우 만족스러운 분석결과를 얻을 수 있으며, 그 결과로서 향후 형광 X-선 분석기를 이용한 응용범위가 크게 확대되는 효과를 기대할 수 있다.As shown in the examples, after preparing the sample using the excitation method, when quantitatively analyzing the content of the chlorine ions contained in the trace by fluorescence X-ray analysis, the analysis was performed using the analysis method according to the present invention. When performed, a very satisfactory analysis result can be obtained, and as a result, an effect of greatly expanding the application range using a fluorescent X-ray analyzer can be expected.

Claims (1)

여지법을 이용하여 형광 X-선 분석법으로 용액 중에 미량 함유되어 있는 염소이온을 질산은과 반응시켜 정량 분석함에 있어서, ClKα와 AgLα의 강도를 동시에 측정하여 AgLα의 강도를 내부표준으로 사용하여 표준용액을 이용하여 염소이온의 농도 대 ClKα/AgLα 강도와의 검량곡선을 작성 한 후, 분석하고자 하는 미지 시료용액의 경우도 동일한 방법으로 시료 조제를 하고 나서 ClKα/AgLα의 강도를 측정하고, 앞서 작성된 검량곡선을 이용하여 정량분석함을 특징으로 하는 여지법을 이용한 용액 중의 미량 염소이온 형광 X-선 분석방법.In quantitative analysis by reacting silver nitrate with chlorine ions contained in the solution by fluorescence X-ray analysis using excitation method, the intensity of ClKα and AgLα were measured simultaneously and the intensity of AgLα was used as internal standard. After preparing the calibration curve between the concentration of chlorine ion and the ClKα / AgLα intensity, prepare the sample solution in the same way for the unknown sample solution to be analyzed and then measure the intensity of ClKα / AgLα, Trace chlorine ion fluorescence X-ray analysis method in solution using the method characterized in that the quantitative analysis using.
KR1019940040298A 1994-12-31 1994-12-31 Fluorescent x-ray analysis method of micro-chlorine ion using paper disc method KR0158562B1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101368512B1 (en) * 2012-04-25 2014-02-28 현대제철 주식회사 Method for manufacturing test sheet for analysis on chlorine content

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101368512B1 (en) * 2012-04-25 2014-02-28 현대제철 주식회사 Method for manufacturing test sheet for analysis on chlorine content

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