Quantitative method

Abstract

The purpose of the present invention is to provide a method for more accurately quantifying a test substance in a measurement system in which the amount of the test substance is increased or decreased in a measurement device when measuring a sample. A quantification method for quantifying a substance to be detected in a sample containing the substance to be detected, the method being characterized by comprising: (1) a step for measuring the same sample a plurality of times using a measurement device to obtain a plurality of quantitative values for the substance to be detected in the sample; and (2) a step for calculating, from the plurality of quantitative values, an increase / decrease amount of the test substance by the measurement device, and correcting at least one of the plurality of quantitative values by means of the increase / decrease amount to obtain a real quantitative value of the test substance.

Description

Technical Field

[0001] This invention relates to a quantitative method for measurement systems in which the quantitative value of the substance originally present in the sample cannot be obtained due to changes in the amount of the substance being tested within the measurement system during sample determination. Background Technology

[0002] As an example, consider substances with extremely high hydrolytic properties that will hydrolyze once the sample comes into contact with water adsorbed on the inner wall of the measurement system, such as a pool or pipe, during the measurement.

[0003] Such substances inevitably contain hydrolysis products as impurities due to their inherent properties. When these hydrolysis products are the analyte, if the sample is introduced into the measuring device for testing, the analyte will be generated due to water adsorbed onto the inner wall of the pipe or container. This generated analyte becomes the background, and the quantitative value of the analyte obtained will be greater than the amount of analyte originally present in the sample.

[0004] In order to accurately quantify such a substance, the water adsorbed on the inner wall of the measuring device should be completely removed or removed to a degree that does not affect quantification and thus does not generate a background.

[0005] As components constituting a measurement system including pipes, metal is generally considered to be predominant, depending on the design of the measuring device, considering pressure resistance and heat resistance. There are documents demonstrating how heating the components from 120°C to 150°C can cause water adsorbed on the metal to detach from its surface (see, for example, Non-Patent Literature 1 and 2). However, it is extremely difficult to confirm that the water has been completely removed or reduced to a level that does not affect quantification. Furthermore, there are concerns that heating the components may cause mechanical changes in the measurement system, such as optical axis shift, which could affect the quantification results. Therefore, it is impractical to completely remove water adsorbed on the inner wall of the measuring device or to a level that does not affect quantification and thus eliminates the basis.

[0006] On the other hand, methods for reducing background during measurement were also examined. For example, Patent Documents 1 and 2 describe methods for reducing substances present around the light source and detector that cause background in the spectrophotometric analysis of gases. These methods are based on the premise that the analyte and the background-causing substances exist in different spaces. However, the technical problem of this invention is that the analyte and the background exist in the same space. Therefore, in this method, if the signal originating from the background is reduced, the signal originating from the analyte will also be reduced simultaneously, making quantification difficult.

[0007] Furthermore, Patent Document 3 proposes a method for reducing background signals. In order to reduce the background during measurement, pressure is applied to the gas used as the analyte in gas spectrophotometry, thereby reducing the background signal. This method requires the analyte and the background to exist in different spaces. When the analyte and the background exist in the same space, reducing the background signal will also reduce the signal originating from the analyte, thus making quantification impossible. Moreover, this method is limited to gases, thus restricting its application.

[0008] Existing technical documents

[0009] Patent documents

[0010] Patent Document 1: Japanese Patent Application Publication No. 9-005233

[0011] Patent Document 2: Japanese Patent Application Publication No. 2011-179942

[0012] Patent Document 3: Japanese Patent No. 4715759

[0013] Non-patent literature 1: Journal of the Vacuum Society of Japan, 2010, Vol. 53, p. 527

[0014] Non-Patent Literature 2: Surfaces and Vacuum, 2018, Vol. 61, p. 27 Summary of the Invention

[0015] (a) Technical problems to be solved

[0016] As mentioned above, when quantifying highly hydrolyzable analytes, the measurement must be performed with water adsorbed on the inner walls of the measuring apparatus, such as the pipes or containers in contact with the sample. In this case, if the amount of background gas generated, i.e., the increase or decrease in the amount of the analyte, were known, the obtained quantitative value could be corrected based on this increase or decrease, thereby enabling quantification of the analyte originally contained in the sample. However, in reality, the increase or decrease is unknowable, therefore quantification of the analyte is impossible.

[0017] Furthermore, in quantification using liquid chromatography, there is a problem where analytes, such as the packing material adsorbed within the chromatographic column, cannot be accurately quantified. To accurately quantify such analytes, manufacturers are working on reducing adsorption through surface treatment of the packing material. However, depending on the type of analyte, adsorption may be unavoidable, thus preventing accurate quantification.

[0018] The purpose of this invention is to solve the above-mentioned problems and provide a method for more accurately quantifying the substance being tested in a testing system where the amount of the substance being tested increases or decreases within the testing device during sample testing.

[0019] (II) Technical Solution

[0020] To address the aforementioned technical problems, the present invention provides a quantitative method for quantifying a substance in a sample containing the substance to be tested, characterized by comprising:

[0021] (1) A process of performing multiple measurements on the same sample using a measuring device to obtain multiple quantitative values ​​of the substance being tested in the sample; and

[0022] (2) The process of calculating the increase or decrease of the substance being tested caused by the measuring device from the plurality of quantitative values, and using the increase or decrease to correct at least one of the plurality of quantitative values ​​to obtain the true quantitative value of the substance being tested.

[0023] Therefore, in a measurement system where the amount of the substance being tested increases or decreases within the measuring device during sample determination, the substance being tested can be quantified more accurately.

[0024] Furthermore, the test substance in the sample can be determined using a single measuring device.

[0025] Alternatively, multiple measuring devices can be used to measure the substance being tested in the sample.

[0026] In the quantitative method of the present invention, the number of measuring devices is not limited to one, but can be multiple.

[0027] In addition, multiple measuring devices of the same specifications can be used to measure the substance being tested in the sample.

[0028] Alternatively, multiple measuring devices of different specifications can be used to measure the substance being tested in the sample.

[0029] In the quantitative method of the present invention, when multiple measuring devices are used, the specifications of each device may be chosen to be the same or different.

[0030] In addition, a gas cell can be used to determine the substance being tested in the sample.

[0031] Alternatively, a liquid cell can be used to determine the substance being tested in the sample.

[0032] In the quantitative method of the present invention, there are no particular restrictions on the morphology of the sample.

[0033] The procedure (1) can also be performed using a chromatographic method selected from liquid chromatography, ion chromatography and gas chromatography, and using multiple chromatographic columns.

[0034] At this point, the multiple chromatographic columns can be connected in series or in parallel for use.

[0035] The quantitative method of the present invention can be applied, for example, to quantitative analysis using chromatography.

[0036] (III) Beneficial Effects

[0037] According to the present invention, when the analyte deteriorates within the measuring device during sample determination or when the analyte is adsorbed into the column chromatography packing material, the analyte can be quantified more accurately. Attached Figure Description

[0038] Figure 1 This is an example of the quantitative method of the present invention, in which the same pool was used in the first and second measurements.

[0039] Figure 2 This is an example of the quantitative method of the present invention, in which different cells were used in the first and second measurements.

[0040] Figure 3 This is an example of the quantitative method of the present invention, which is an example of connecting two gas cells in series.

[0041] Figure 4 This is an example of the quantitative method of the present invention, which is an example of the procedure of measuring using infrared spectroscopy and a gas cell.

[0042] Figure 5 As an example of the quantitative method of the present invention, it is an example of connecting three or more gas cells in series.

[0043] Figure 6 As an example of the quantitative method of the present invention, it is an example of connecting two chromatographic columns of the same length in series in liquid chromatography and connecting a detector to the rear of each column.

[0044] Figure 7 As an example of the quantitative method of the present invention, it is an example of connecting two chromatographic columns of different lengths in series in liquid chromatography and connecting a detector to the rear of each column.

[0045] Figure 8 As an example of the quantitative method of the present invention, it is an example of connecting two chromatographic columns of different lengths in parallel and connecting detectors to their respective ends in liquid chromatography.

[0046] Figure 9 As an example of the quantitative method of the present invention, it is an example of connecting two chromatographic columns of different lengths in parallel and connecting them to a detector via a six-way valve in liquid chromatography. Detailed implementation mode

[0047] As described above, it is desired to develop a method for more accurately quantifying a test substance in a measurement system in which the amount of the test substance increases or decreases in a measurement device during sample measurement.

[0048] The inventor of the present application conducted in-depth research to achieve the above object, and examined a quantification method in which the increase or decrease amount of the test substance was calculated from the differences (Japanese: differences) of multiple quantification values obtained by measuring the same sample multiple times, and the quantification value was corrected using the increase or decrease amount to obtain the true quantification value.

[0049] That is, the present invention is a quantification method for quantifying the test substance in a sample containing the test substance, characterized by including: (1) a step of measuring the same sample multiple times using a measurement device to obtain multiple quantification values of the test substance in the sample; and, (2) a step of calculating the increase or decrease amount of the test substance caused by the measurement device from the multiple quantification values, and correcting at least one of the multiple quantification values using the increase or decrease amount to obtain the true quantification value of the test substance.

[0050] Hereinafter, the embodiments of the present invention will be described with reference to the drawings, but the present invention is not limited thereto.

[0051] (First aspect)

[0052] In the first aspect of the quantification method of the present invention, one measurement device is used to measure the test substance in the sample. In addition, this aspect can also be applied to any one of a liquid cell and a gas cell.

[0053] Preliminary experiment

[0054] Figure 1 An example of measuring a liquid sample using one liquid cell is shown. The same liquid cell A is used in the first and second measurements, and the increase or decrease amount of the test substance in the first and second measurements must be the same. For this reason, it is necessary to perform the same cleaning or pretreatment on cell A before the second measurement as that performed before the first measurement. In addition, it is also necessary to confirm in advance the reproducibility of the measurement after this cleaning or pretreatment.

[0055] Step (1)

[0056] After this preliminary experiment, the quantitative value A1 of the analyte in the sample is obtained by measuring the sample in cell A. Next, the measured sample is temporarily removed, and cell A is cleaned or pretreated. Then, the measured sample is placed back into cell A and measured again to obtain the quantitative value A2 of the analyte in the sample. Furthermore, the instruments used when removing the measured sample, such as those using fluoropolymers or instruments with passivated inner surfaces, are designed to prevent sample deterioration.

[0057] Process (2)

[0058] Next, the increase or decrease in the amount of the substance being tested caused by the measuring device (cell A) is calculated from multiple quantitative values ​​(quantitative values ​​A1, A2) in the following manner. The calculated increase or decrease is used to correct the quantitative values ​​A1 and / or A2 to obtain the true quantitative value of the substance being tested.

[0059] At this point, the first quantitative value A1 is expressed as follows:

[0060] ■ Quantitative value A1 = Amount of the substance originally present in the sample + Amount of increase or decrease... Equation (17).

[0061] Since the increase or decrease in the amount of the analyte is the same in the first and second measurements, the quantitative value A2 of the second measurement is expressed in the following reverse form:

[0062] ■ Quantitative value A2 = Quantitative value A1 + Increase / Decrease

[0063] =Amount of the analyte originally present in the sample + Increase / Decrease + Increase / Decrease

[0064] = Amount of the substance being tested that was originally present in the sample + 2 × Increase / Decrease... Equation (18).

[0065] Subtract equation (17) from equation (18), and swap the left and right sides.

[0066] ■ Increase / decrease = Quantitative value A2 - Quantitative value A1 • Equation (19).

[0067] Furthermore, by transforming equation (17),

[0068] ■ The amount of the substance originally present in the sample = quantitative value A1 - increase / decrease... Equation (20)

[0069] Substituting equation (19) into the right side, the amount of the substance being tested that was originally present in the sample is calculated as follows:

[0070] ■ The amount of the substance originally present in the sample = Quantitative value A1 - (Quantitative value A2 - Quantitative value A1)

[0071] =2 × Quantitative value A1 - Quantitative value A2

[0072] The first aspect of the present invention can be expressed, for example, in the following manner.

[0073] A quantitative method for quantifying a substance in a sample containing the substance to be tested, characterized by comprising:

[0074] (1) The process of adding the sample to the measuring device A and using the measuring device A to obtain the quantitative value A1 of the substance being tested in the sample;

[0075] (2) The process of adding the sample supplied in step (1) back into the measuring device A, and using the measuring device A to obtain the quantitative value A2 of the substance being tested in the sample; and

[0076] (3) The process of calculating the difference between the quantitative value A1 and the quantitative value A2, taking the difference as the increase or decrease A of the substance being tested caused by the measuring device A, and using the increase or decrease A to correct the quantitative value A1 and / or the quantitative value A2 to obtain the true quantitative value of the substance being tested.

[0077] (Option 2)

[0078] In a second embodiment of the quantitative method of the present invention, multiple measuring devices of different specifications are used to determine the analyte in the sample. Furthermore, this method can also be applied to any type of liquid cell or gas cell.

[0079] Process (1)

[0080] Figure 2 An example is shown where two liquid cells, A and B, are used to measure a liquid sample. (Compared to...) Figure 1 The difference lies in the use of liquid cell A in the first determination and liquid cell B in the second. Furthermore, the instruments used for recovery, such as those using fluoropolymers or with passivated inner surfaces, ensure that the sample does not deteriorate during recovery. This is different from... Figure 1 The same. Using two spectrophotometers, one can measure liquid cell 1, and the other can measure liquid cell 2.

[0081] For example, two measuring devices can be designated as tanks A and B, respectively, with the liquid or gas tanks. First, tank A is used to measure the sample to obtain a quantitative value 1A. Then, tank B is used to measure the same sample to obtain a quantitative value 1B. In this case, the increase or decrease in the amount of the analyte produced in tank A is designated as increase / decrease A, and the increase or decrease in the amount of the analyte produced in tank B is designated as increase / decrease B. Alternatively, instead of the above, tank B can be used to measure the sample to obtain a quantitative value 2B. Then, tank A is used to measure the same sample to obtain a quantitative value 2A. In this case, the increase or decrease in the amount of the analyte produced in tank A is designated as increase / decrease A, and the increase or decrease in the amount of the analyte produced in tank B is designated as increase / decrease B. In this case, tanks A and B, of course, need to be cleaned or pretreated to ensure that the increase or decrease in the amount of the analyte is the same in the first and second measurements.

[0082] Process (2)

[0083] Next, the increase or decrease in the amount of the tested substance A and B brought about by the measuring device is calculated from multiple quantitative values ​​(quantitative values ​​1A, 1B, 2B, 2A) in the following manner. The calculated increase or decrease is used to correct each quantitative value to obtain the true quantitative value of the tested substance.

[0084] When measurements are performed in the order of A and B, it is denoted as (A→B); when measurements are performed in the order of B and A, it is denoted as (B→A).

[0085] ■ Quantitative value A (A→B) = Amount of the substance originally present in the sample + Amount increase / decrease A・・・Equation (1).

[0086] Transform equation (1) to...

[0087] ■ The amount of the substance originally present in the sample = quantitative value A (A→B) - increase / decrease A... Equation (2)

[0088] also,

[0089] ■ Quantitative value B(A→B) = Quantitative value A(A→B) + Increase / decrease B... Equation (3),

[0090] Transform equation (3) to...

[0091] ■ Increase / decrease B = Quantitative value B(A→B) - Quantitative value A(A→B) ・・・Equation (4)

[0092] Therefore, the increase or decrease B can be determined from the results obtained by measuring in the order of A and B.

[0093] On the other hand, when measured in the order of B and A,

[0094] ■ Quantitative value B (B→A) = Amount of the analyte originally present in the sample + Increase / decrease B... Equation (5),

[0095] Transform Equation 5

[0096] ■ The amount of the substance originally present in the sample = quantitative value B (B→A) - increase / decrease B・・・Equation (6).

[0097] By substituting the increase or decrease B obtained from equation (4), the amount of the substance being tested that originally existed in the sample can be determined.

[0098] Then,

[0099] ■ Quantitative value A(B→A) = Quantitative value B(B→A) + Increase / decrease A... Equation (7),

[0100] Transform equation (7) to...

[0101] ■ Increase / decrease A = Quantitative value A(B→A) - Quantitative value B(B→A) ・・・Equation (8),

[0102] Substituting the increase or decrease A into equation (2), the amount of the substance being tested that originally existed in the sample can be determined.

[0103] For the amount of the analyte originally present in the sample, since two values ​​can be obtained from equations (2) and (6), the reliability of the quantitative value can be confirmed by comparing them. In addition, when the analyte does not deteriorate in the measuring device during the measurement, the quantitative values ​​A (A→B), B (A→B), A (B→A), and B (B→A) are all the same, and the increase or decrease in A and B is 0.

[0104] The second aspect of the present invention can be expressed, for example, in the following manner.

[0105] A quantitative method for quantifying a substance in a sample containing the substance to be tested, characterized by comprising:

[0106] (1A) The process of adding the sample to the measuring device A and using the measuring device A to obtain the quantitative value 1A of the substance being tested in the sample;

[0107] (1B) The process of adding the sample supplied to the process (1A) into the measuring device B and using the measuring device B to obtain the quantitative value 1B of the substance to be tested in the sample.

[0108] (2B) A step in which a new sample is added to the measuring device B, different from the samples supplied to steps (1A) and (1B), and the measuring device B is used to obtain a quantitative value 2B of the analyte in the sample; and

[0109] (3) The process of calculating the difference between the quantitative value 1A and the quantitative value 1B, taking the difference as the increase or decrease B of the substance being tested caused by the measuring device B, and using the increase or decrease B to correct the quantitative value 2B to obtain the true quantitative value of the substance being tested.

[0110] Preferably, after the step (2B), the method includes: (2A) adding the sample supplied to the step (2B) to the measuring device A, and using the measuring device A to obtain a quantitative value 2A of the substance being tested in the sample.

[0111] At this time, it is preferable to perform step (3') simultaneously with step (3): calculate the difference between the quantitative value 2B and the quantitative value 2A, take the difference as the increase or decrease A of the substance being tested caused by the measuring device A, and use the increase or decrease A to correct the quantitative value 1A, thereby obtaining the true quantitative value of the substance being tested.

[0112] (Option 3)

[0113] The third aspect of the quantitative method of the present invention is a quantitative method for situations where the increase or decrease obtained from multiple measurements of the same sample is the same in the first measurement and subsequent measurements (e.g., when multiple measuring devices of the same specifications are used to measure the analyte in the sample). Furthermore, this method can also be applied to any of the liquid or gas cells.

[0114] Process (1)

[0115] Through preliminary experiments, it is known that when the increase or decrease obtained from multiple measurements of the same sample is the same in the first measurement and the second and subsequent measurements (for example, when measuring device A and measuring device B are of the same specification, and the increase or decrease brought by measuring device A is the same as the increase or decrease brought by measuring device B), as described in the second scheme, the amount of the substance originally present in the sample is determined in one set of measurements (only A→B or B→A) without changing the measurement order, in the order of A, B and B, A.

[0116] First, the sample is quantitatively measured to obtain the quantitative value 1 of the analyte. At this time, the amount of the analyte increases or decreases within the measurement system, resulting in a change of 1. Therefore, this quantitative value 1 is the difference between the amount of the analyte originally present in the sample and the change of 1, which represents the amount of the analyte after its alteration within the measurement device. Furthermore, if the change of 1 is positive when the amount of the analyte increases, then...

[0117] ■Quantitative value 1 = Amount of the substance originally present in the sample + Increase / decrease 1... Equation (9).

[0118] Transform equation (9) to...

[0119] ■The substance originally present in the sample = quantitative value 1 - increase / decrease 1... Equation (10),

[0120] Since a quantitative value of 1 has been obtained, if the increase or decrease of 1 is known, the substance to be tested that was originally present in the sample can be quantified.

[0121] Next, the sample from which the first quantitative determination was performed was removed from the test system and measured again under the same conditions to obtain quantitative value 2. This same condition refers to the condition under which the increase or decrease obtained from multiple measurements of the same sample is the same in the first measurement and the second and subsequent measurements (e.g., the increase or decrease caused by measuring device A is the same as the increase or decrease caused by measuring device B). Quantitative value 2 is the amount of the analyte present in the sample after the first measurement, i.e., the amount obtained by adding the increase or decrease 2, which represents the increase or decrease of the analyte in the measuring device during the second measurement, to quantitative value 1.

[0122] Process (2)

[0123] Right now,

[0124] ■ Quantitative value 2 = Quantitative value 1 + Increase / decrease amount 2 ・・・ Formula (11).

[0125] In this case, the increase / decrease amount 2 in the second measurement is the same as the increase / decrease amount 1 in the first measurement, therefore

[0126] ■ Increase / decrease 2 = Increase / decrease 1・・・Equation (12).

[0127] Substituting it into equation (11),

[0128] ■ Quantitative value 2 = Quantitative value 1 + Increase / decrease 1 ・・・Equation (13)

[0129] Furthermore, substituting equation (9) into the quantitative value 1 in equation (13),

[0130] ■Quantitative value 2 = Amount of the substance originally present in the sample + Increase / Decrease 1 + Increase / Decrease 1... Equation (14).

[0131] Subtract equation (9) from equation (14).

[0132] ■Quantitative value 2 - Quantitative value 1 = Increase / decrease 1...Equation (15),

[0133] The increase or decrease 1 is calculated from the quantitative values ​​obtained from the two measurements. By exchanging the right and left sides of equation (15),

[0134] ■ Increase / decrease 1 = Quantitative value 2 - Quantitative value 1... Equation (16).

[0135] Substituting it into equation (10),

[0136] ■The substance originally present in the sample = Quantitative value 1 - (Quantitative value 2 - Quantitative value 1)

[0137] =Quantitative value 1 - Quantitative value 2 + Quantitative value 1

[0138] =2 × Quantitative value 1 - Quantitative value 2.

[0139] Quantitative values ​​1 and 2 can be obtained in the form of measurement data, thus allowing for the quantification of the amount of the analyte originally present in the sample. Furthermore, if the analyte remains unchanged within the measuring device during the measurement, the increase / decrease 1 and increase / decrease 2 are 0, and the quantitative values ​​1 and 2 are the same.

[0140] The third aspect of the present invention can be expressed, for example, in the following manner.

[0141] A quantitative method for quantifying a substance in a sample containing the substance to be tested, characterized in that...

[0142] (1) The process of adding the sample to the measuring device A and using the measuring device A to obtain the quantitative value A of the substance being tested in the sample;

[0143] (2) The step of adding the sample supplied in step (1) to a measuring device B of the same specifications as the measuring device A, and using the measuring device B to obtain the quantitative value B of the substance being tested in the sample; and

[0144] (3) The process of calculating the difference between the quantitative value A and the quantitative value B, taking the difference as the increase or decrease of the substance being tested caused by the measuring devices A and B respectively, and using the increase or decrease to correct the quantitative value A and / or the quantitative value B to obtain the true quantitative value of the substance being tested.

[0145] Figure 1 and 2 In cases where the apparatus used for processing the sample in the first determination and for recovering the sample after the first determination are to prevent deterioration of the analyte during sample processing and recovery, for example, using fluoropolymers or apparatus with passivated inner surfaces, the deterioration of the analyte can be avoided in the aforementioned procedures if the procedures are performed in a manner that prevents the sample from deteriorating during sample processing and recovery. However, even if deterioration cannot be avoided, it can be assumed that the quantitative value of the increase or decrease in all procedures from sample processing to the first determination is measured in the first determination, and the quantitative value of the increase or decrease in sample recovery from the first determination to the second determination is measured in the second determination. In this case, the same apparatus should be used for processing the sample in the first determination and for recovering the sample after the first determination to ensure that the increase or decrease in these procedures are performed in the same manner. Furthermore, the reproducibility of the quantitative value including the recovery operation needs to be confirmed in advance.

[0146] (Option 4)

[0147] In the quantitative method of the present invention, such as Figure 3 As shown, measurements can also be performed using a spectrophotometric method by connecting two spectrophotometers with a gas cell in series.

[0148] For example, such as Figure 3 As shown, two spectroscopic devices using a gas cell are connected in series to achieve [the desired effect]. Figure 4 The steps shown are for quantifying hydrogen chloride (the analyte) in dichlorosilane (sample). Figure 4 As shown, the quantitative method of the present invention consists of drying inside the measuring device based on vacuum (step 1), drying inside the measuring device based on drying gas (step 2), introducing the sample into the measuring device (step 3), absorbance measurement (step 4), and displacement of the measuring device interior by the drying gas (step 5). Each step will be described in detail below.

[0149] (Step 1: Drying inside the measuring device based on vacuum)

[0150] Prepare a vacuum pump, connect it to the measuring device, and evacuate the internal components. For example, you can heat the pipes, mass flow controller, and valves to 40°C while evacuating until the vacuum level reaches -90 kPa(G).

[0151] (Step 2: Drying inside the measuring device based on dry gas)

[0152] For example, dry nitrogen gas (Grade 3, dew point -70℃, H2O concentration 2.55ppm) already filled into the gas cylinder is introduced into the measuring device at a pressure of 200kPa and a flow rate of 4 to 5 liters / minute to dry the inside of the measuring device overnight (about 10 hours).

[0153] (Step 3: Introduce the sample into the measuring device)

[0154] Dichlorosilane gas is introduced into the measuring device. For example, it is introduced into the measuring device at a pressure of 50~100 kPa at a rate of 2~3 liters / minute.

[0155] (Step 4: Absorbance Measurement)

[0156] The absorbance of hydrogen chloride in dichlorosilane gas filled into a gas cylinder was measured. For example, the 2981 cm⁻¹ absorbance is considered to be the stretching vibration mode of H-Cl originating from the analyte. -1 The peak of hydrogen chloride does not overlap with the infrared absorption peak of dichlorosilane and exists in its valley, thus allowing for quantification unaffected by dichlorosilane and not limited to that peak. Immediately after sample introduction, the absorbance of the hydrogen chloride peak is continuously measured; if it stabilizes at a constant value, that value is used for quantification.

[0157] (Step 5: Replacement of the interior of the measuring device with drying gas)

[0158] After the measurement, the dichlorosilane gas is removed from the measuring device. For example, after evacuating to a vacuum level of -90 kPa(G), dry nitrogen gas is introduced into the measuring device at a pressure of 200 kPa and a flow rate of 4-5 L / min to replace the interior of the measuring device. The peak of dichlorosilane (2237 cm⁻¹) is then continuously measured immediately after the introduction of dry nitrogen gas. -1 The absorbance of the area (near the peak) was measured, and substitution was performed continuously until the peak could not be detected.

[0159] In addition, at this time, such as Figure 5 As shown, three or more infrared spectrometers using gas cells can be connected in series. The increase or decrease is calculated by subtracting the quantitative value obtained from the preceding infrared spectrometer from the quantitative value obtained from the current spectrometer. The quantitative value is then corrected using this increase or decrease, which is the same as when there are two spectrometers.

[0160] (Fifth Option)

[0161] Figure 6 This is an example of using two columns of identical diameter, length, and packing material in liquid chromatography, connected in series and with detectors connected to their respective ends. The increase or decrease is calculated by subtracting the quantitative value obtained from detector 1 from the quantitative value obtained from detector 2. This increase or decrease is then used to correct the quantitative value, as in the previously described example. However, differential refractive index (RI) detectors used in liquid chromatography typically have low pressure tolerance. For this application, pressure tolerance needs to be confirmed. Since the diameter, length, and packing material are identical, it is ideally assumed that the increase or decrease in the analyte produced during passage through the two columns will be the same, but it is desirable to confirm this before implementation. Therefore, each column is connected individually, and the quantitative value is confirmed. If the quantitative values ​​differ, it indicates that the increase or decrease in the analyte is different. The quantitative value can be obtained by swapping the ends of the two columns and performing measurements, as described above.

[0162] Figure 7 This example illustrates a liquid chromatography method where two columns of the same diameter and packing material but different lengths are connected in series, with detectors connected to their respective ends. In this case, only the lengths differ, and it is assumed that the increase or decrease in the amount of analyte produced during passage through each column is ideally proportional to its length; however, it is desirable to verify this before implementation. This can be achieved by connecting each column individually and confirming the quantification values.

[0163] Figure 8This example illustrates a liquid chromatography method using two columns of the same diameter and packing material but different lengths connected in parallel, each with a detector connected to its downstream end. Since no back pressure is applied to the detector, there is no need to worry about the pressure resistance issues encountered when using an RI detector. While the difference in length is the primary concern, it is assumed that the increase or decrease in the amount of analyte produced during passage through each column is ideally proportional to its length; however, this should be verified before implementation. This can be achieved by connecting each column individually and verifying the quantification values. Furthermore, as... Figure 9 As shown in the parallel connection diagram, two chromatographic columns of different lengths can also be connected in parallel and connected to a detector via a six-way valve.

[0164] In addition, in this invention, the process (1) can be performed using multiple chromatographic columns selected from liquid chromatography, ion chromatography, and gas chromatography. In this case, multiple chromatographic columns can be connected in series or in parallel for use.

[0165] Example

[0166] The following examples and comparative examples of the present invention are shown to illustrate the present invention in more detail, but the present invention is not limited thereto.

[0167] (Example)

[0168] Prepare two identical infrared spectrometers, designated as apparatus A and B. To remove moisture adsorbed on the inner walls of the apparatus and pipes in apparatus A, heat each pipe to 40°C while simultaneously purging with dry nitrogen gas (dew point temperature -70°C, moisture content 2.55 ppm) for 1 minute. Then, perform 30 cycles of vacuum purging for 10 minutes each. It takes approximately 5 hours to reach a vacuum level above -90 kPa(G). Then, without breaking the vacuum, introduce a standard gas (nitrogen gas containing 0.1, 0.2, 0.5, 1.0, and 5.0 ppm of hydrogen chloride) for measurement, and construct a standard curve. Next, without breaking the vacuum, introduce dichlorosilane gas and measure the hydrogen chloride peak over time. After the measured value stabilizes, quantify the hydrogen chloride using the standard curve. Perform the same operation in apparatus B to quantify the hydrogen chloride, confirming that the same quantitative value was obtained in apparatus A and B.

[0169] Next, devices A and B were connected in series. To remove moisture adsorbed on the inner walls of the devices and pipes, each pipe was heated to 40°C while purging with dry nitrogen gas (dew point temperature -70°C, moisture content 2.55 ppm) for 1 minute. Then, a cyclic purging process of 30 cycles of vacuuming for 10 minutes each was performed. It took approximately 5 hours to reach a vacuum level of -90 kPa(G). Then, without breaking the vacuum, standard gases (nitrogen gas containing 0.1, 0.2, 0.5, 1.0, and 5.0 ppm of hydrogen chloride) were introduced for measurement, and standard curves were prepared using devices A and B respectively. Then, without breaking the vacuum, dichlorosilane gas was introduced, and the peak of hydrogen chloride was measured over time. After the measured value stabilized, the standard curve was used to quantify the hydrogen chloride. The results of quantifying hydrogen chloride by changing batches (implementation numbers 1 to 11) are shown in Table 1. The amount of hydrogen chloride in each batch fluctuates between 0.026 ppm and 1.083 ppm, but the value of apparatus B to apparatus A, that is, the amount of hydrogen chloride generated in the system of apparatus B during the measurement (increase or decrease), is almost constant.

[0170] [Table 1]

[0171]

[0172] Next, with devices A and B connected in series, the results of batch quantification using the same method as before are shown in Table 2 (Implementation Nos. 12-13). The amount of hydrogen chloride in each batch fluctuated between 0.463 ppm and 0.815 ppm, but the value of device A-device B, i.e., the amount of hydrogen chloride generated in the system of device A during the measurement (increase or decrease), was almost constant and was approximately the same as when devices A and B were connected in series, confirming that there was no effect caused by the order of the devices.

[0173] [Table 2]

[0174]

[0175] As described above, the quantitative method of the present invention can obtain the increase or decrease of the substance being tested with good reproducibility. Therefore, by correcting the quantitative value using the increase or decrease, a true quantitative value (a more accurate quantitative value) can be obtained.

[0176] (Comparative Example)

[0177] In the preceding embodiment, when two infrared spectrometers were connected in series, it was assumed that the measurement result of the preceding device A was the same as that obtained using existing methods, and therefore its data was used as a comparative example. The measurement sequence and the results obtained were the same as in the embodiment, but the amount of hydrogen chloride generated in the system of device A during the measurement was unclear. Therefore, the quantitative value of hydrogen chloride in dichlorosilane had to be directly adopted from the quantitative value of hydrogen chloride measured in device A. The amount of hydrogen chloride in dichlorosilane obtained in the comparative example is shown in Table 3, which is larger than the value obtained in Table 1 and was overestimated. Moreover, in the comparative example, since the amount of hydrogen chloride generated in the system of device A could not be quantified, the amount of hydrogen chloride in dichlorosilane could not be quantitatively displayed, and it could only be said to be below a certain value.

[0178] [Table 3]

[0179]

[0180] Furthermore, the present invention is not limited to the above-described embodiments. For example, although two infrared beam splitters were used in the embodiments, but... Figure 2 In the first and second measurements, the light source and detector can be the same. That is, the light source of an infrared spectrometer can be incident on cells A and B and measurements can be performed.

[0181] Furthermore, when the results of analysis of the sample using an infrared spectrometer are affected by moisture remaining in the system through which the sample passes, more satisfactory results can be obtained by further heating the pipe or gas cell used to introduce the sample and introducing high-purity dry nitrogen to thoroughly remove the moisture adsorbed on the inner wall. Although this is not currently possible with technology, heating the pipe or gas cell used to introduce dichlorosilane gas to above 120°C to 150°C and introducing high-purity dry nitrogen to thoroughly remove the moisture adsorbed on the inner wall will reduce the blank value and lower the limit of quantitation and the limit of detection. When heating at high temperatures, it is preferable to insulate the detector and the cell in a manner that does not affect the infrared spectrometer used as a detector. In addition, if a gas cell, pipe, and window material that can be further evacuated to a high vacuum can be used, the moisture remaining in the system can be further reduced. Therefore, this situation can also reduce the blank value, allowing for more accurate measurements and more satisfactory results. At this time, it can also be used to quantify hydrogen chloride in trichlorosilanes or tetrachlorosilanes, which have a higher boiling point than dichlorosilanes.

[0182] This specification includes the following inventions.

[0183] [1] A quantitative method for quantifying a substance in a sample containing a substance to be tested, characterized in that it includes: (1) a step of performing multiple measurements on the same sample using a measuring device to obtain multiple quantitative values ​​of the substance to be tested in the sample; and (2) a step of calculating the increase or decrease of the substance to be tested caused by the measuring device from the multiple quantitative values, and correcting at least one of the multiple quantitative values ​​using the increase or decrease to obtain the true quantitative value of the substance to be tested.

[0184] [2]: The quantitative method described in [1] above is characterized in that the substance to be tested in the sample is measured using a measuring device.

[0185] [3]: The quantitative method described in [1] above is characterized in that multiple measuring devices are used to measure the substance to be tested in the sample.

[0186] [4]: According to the quantitative method described above [3], the characteristic is that multiple measuring devices of the same specification are used to measure the substance to be tested in the sample.

[0187] [5]: The quantitative method described in [3] above is characterized in that multiple measuring devices of different specifications are used to measure the substance to be tested in the sample.

[0188] [6]: The determination of the test substance in the sample is performed using a gas cell according to the quantitative method described in any one of [1] to [5] above.

[0189] [7]: The determination of the test substance in the sample is performed using a liquid cell according to the quantitative method described in any one of [1] to [5] above.

[0190] [8]: The quantitative method according to any one of [1] to [7] above is characterized in that the step (1) is performed using multiple chromatographic columns by means of a chromatographic method selected from liquid chromatography, ion chromatography and gas chromatography.

[0191] [9]: The quantitative method described in [8] above is characterized in that the multiple chromatographic columns are connected in series or in parallel for use.

[0192] Furthermore, this invention is not limited to the above-described embodiments. The above embodiments are illustrative examples, and any technical solutions having a substantially identical structure and achieving the same effect as the technical concept described in the claims of this invention are included within the scope of protection of this invention.

Claims

1. A quantitative method for quantifying a substance in a sample containing the substance to be tested, characterized in that, include: (1) A process of using a measuring device to measure the same sample multiple times to obtain multiple quantitative values ​​of the substance being tested in the sample; and (2) The process of calculating the increase or decrease of the substance being tested caused by the measuring device from the plurality of quantitative values, and using the increase or decrease to correct at least one of the plurality of quantitative values ​​to obtain the true quantitative value of the substance being tested.

2. The quantitative method according to claim 1, characterized in that, The test substance in the sample was determined using a single measuring device.

3. The quantitative method according to claim 1, characterized in that, The test substance in the sample was determined using multiple measuring devices.

4. The quantitative method according to claim 3, characterized in that, The test substance in the sample was determined using multiple measuring devices of the same specification.

5. The quantitative method according to claim 3, characterized in that, The test substance in the sample was determined using multiple measuring devices of different specifications.

6. The quantitative method according to claim 1, characterized in that, The analyte in the sample was determined using a gas cell.

7. The quantitative method according to claim 1, characterized in that, The test substance in the sample is determined using a liquid cell.

8. The quantitative method according to claim 1, characterized in that, The process (1) is performed using multiple chromatographic columns selected from liquid chromatography, ion chromatography and gas chromatography.

9. The quantitative method according to claim 8, characterized in that, The multiple chromatographic columns are connected in series or in parallel for use.

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