JP3242518B2 - Method and apparatus for measuring solution sample - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for measuring a solution sample used in high frequency inductively coupled plasma emission spectroscopy or high frequency inductively coupled plasma mass spectrometry.

[0002]

2. Description of the Related Art In general, high frequency inductively coupled plasma emission spectroscopy (ICP-AES) is a technique in which a sample solution is atomized and injected into the center of a high-temperature plasma of argon generated by high-frequency energy, and light is emitted by elements in the sample. This is a method for quantifying the content of each element by measuring the respective intensities by spectroscopy. In high-frequency inductively coupled plasma mass spectrometry (ICP-MS), a sample solution is atomized and injected into the center of a high-temperature plasma of argon generated by high-frequency energy, and the generated element ions in the sample are analyzed by a mass spectrometer. This is a method of quantifying the content of each element by measuring. These two quantification methods are widely used because many elements can be analyzed simultaneously and have characteristics such as high sensitivity and high accuracy.

[0003] The supply of the sample solution into the plasma is performed by atomizing the sample. The method of atomizing the sample is a spraying method or an ultrasonic method. The atomizing part of the nebulizer sucks up the sample solution by the flow of the argon gas and sprays the sample solution into the chamber, or vibrates the transducer to vibrate the sample solution. Atomize. Among the spray particles, large-diameter particles are excluded, and only small-diameter particles are sent to the plasma by being placed in an air stream. At this time, what is important for maintaining the measurement accuracy is that particles having a certain particle size distribution are supplied at a stable density. The remaining solution accumulates at the bottom while passing through the chamber and is drained from the drain.

In an actual operation, at least several measurements are required in order to prepare a calibration curve and then measure a sample to be quantified. In the meantime, each time one measurement is completed, room temperature water is sprayed instead of the sample solution to wash the nebulizer and the inside of the chamber of the nebulizer.

[0005]

However, when measuring a high-concentration salt solution, salt easily precipitates in the atomization part of the nebulizer, and is completely washed even with room temperature water sprayed alternately with the sample solution. As the measurement is repeated, the precipitated salt gradually accumulates, making it impossible to spray the solution sample constantly, and as a result, the emission intensity and the ionic intensity change with time. For this reason, the argon plasma must be turned off once, the nebulizer body must be removed, and the salt attached to the atomization part of the nebulizer must be removed. Before restarting the measurement, it is necessary to wait for the stability of the apparatus and then to prepare a calibration curve again, which not only complicates the operation but also significantly lowers the working efficiency. Further, the temporal change of the luminescence intensity and the ionic intensity due to salt precipitation lowers the reliability of the calibration curve and makes it difficult to perform highly accurate measurement.

As a means for preventing the precipitation of salt, a method of humidifying argon gas used for spraying has been known. However, although this method is slightly improved, the effect of preventing the luminescence intensity and the ionic intensity from changing with time is insufficient. On the other hand, in order to enhance the effect of removing salts in the atomization part of the nebulizer, it is not possible to use water at a temperature higher than room temperature (hereinafter simply referred to as "warming water") instead of room temperature water sprayed alternately with the sample solution. Had never been done before. The reason is that, as shown in Japanese Patent Application Laid-Open No. 60-73337, it is thought that when spraying heated water, the temperature inside the chamber rises and the spray efficiency of the sample solution changes significantly, so that precise measurement becomes impossible. Because it was.

However, the present inventors have found that spraying heated water with a nebulizer or spraying heated water on an atomizing portion of a nebulizer in a chamber under certain conditions may cause a change in spray efficiency. It has been found that it is possible to prevent the luminescence intensity and the ionic intensity from changing with time without being affected by a decrease in accuracy. Since this method can be performed without removing the nebulizer main body, the measurement time can be significantly reduced.

An object of the present invention is to provide a high-frequency inductively coupled plasma emission spectroscopy or a high-frequency inductively coupled plasma mass spectrometry, which is capable of preventing a change in emission intensity and ionic intensity over time due to the effect of salts deposited on an atomizing portion of a nebulizer, and measuring accuracy. It is an object of the present invention to provide a method and an apparatus for measuring a solution sample capable of improving the measurement time and greatly reducing the measurement time.
The present invention can also be applied to the measurement of a solution sample by another analyzer provided with a nebulizer for atomizing the sample solution.

[0009]

In order to solve the above-mentioned problems, a method and an apparatus for measuring a solution sample according to the present invention include: (1) a method for measuring using a nebulizer for atomizing a sample solution; And heating water is supplied to an atomizing section of the nebulizer. (2) The analyzer is a high-frequency inductively coupled plasma emission spectrometer or a high-frequency inductively coupled plasma mass spectrometer. (3) The solution sample and the warm water are sprayed alternately. (4) The invention is characterized in that warming water introduced from the outside is forcibly sprayed onto the atomizing section of the nebulizer. (5) The spraying of the solution sample and the spraying of warming water in a state where room temperature water is sprayed are performed alternately. (6) The time for passing or blowing the heated water to the atomizing part of the nebulizer is equal to or longer than the time required for the emission intensity or ionic intensity to change and stabilize by switching from the solution sample to the heated water. And (7) The temperature of the heated water is in the range of 30 ° C. or more and the boiling point or less. (8) The heating water is characterized by containing the heating water alone or a mixture of at least one of an inorganic acid, an organic acid and a surfactant. (9) A sample or heated water supply device for performing the solution sample measurement method, wherein the sample supply unit supplies a sample, a heated water tank that stores heated water, the sample supply unit or the heated water supply unit. A suction nozzle that can be selectively immersed in a sample or heated water in a hot water tank, and a suction pump that selectively sucks a sample or heated water from the suction nozzle and supplies the sample or heated water to an atomizing unit of the nebulizer. (10) The sample supply unit has a rotatable turntable and a test tube in which a solution sample is placed and which is detachable from the turntable.

[0010]

According to the method of the present invention, it is possible to reliably remove the salts deposited from the sample solution and adhered to the atomizing portion of the nebulizer. The measurement can be suppressed and highly accurate measurement can be performed. In addition, since this method can be performed without removing the nebulizer, the measurement time can be significantly reduced.

[0011]

Embodiments of the present invention will be described below. The effect is the same whether spraying heated water with a nebulizer or forcibly spraying heated water introduced from the outside into the atomizing part of the nebulizer in the chamber.Cross-flow type, coaxial type, ultrasonic type It has nothing to do with the type of nebulizer. Since the principle of atomizing the sample solution is the same for high-frequency inductively coupled plasma emission spectroscopy and high-frequency inductively coupled plasma mass spectroscopy, cross-flow and coaxial nebulizers are used here for high-frequency inductively coupled plasma emission spectroscopy. An example of a method of spraying warming water by spraying will be described. The measurement of the solution sample is performed by the following procedure, for example, as shown in FIG. Room temperature water is sprayed with a nebulizer, argon plasma is turned on, and left for 15 to 30 minutes to stabilize the high frequency inductively coupled plasma emission spectrometer. Remove the room temperature water or heated water and attach the liquid to be measured. Preliminary spraying is performed for about 20 seconds to stabilize the emission intensity. Perform the measurement. The liquid to be measured is sprayed for about 10 seconds, and the luminescence intensity is measured. The liquid to be measured is removed, and room temperature water or heated water is sprayed until the luminescence intensity becomes constant at around 0 to wash the nebulizer and the inside of the chamber of the nebulizer. The above is repeated.

FIG. 9B schematically shows a change in luminescence intensity when measurement is performed by spraying warm water alternately with the sample solution according to the above procedure. In the following comparative tests, water at 23 ° C. was used as room temperature water. Comparative test 1 Determination of yttrium in zirconia ceramics
The following two methods were used.

Li ₂ B ₄ O ₇ : 1 g is added to 3.6% hydrochloric acid: 1
The sample was dissolved in 00 ml, and 100.0 ppm of Y ₂ O ₃ was added to prepare a sample solution. Using a cross-flow nebulizer, the procedure was performed at a measurement wavelength of 371.03 nm,
The emission intensity of yttrium was measured according to the following. afterwards,
Room temperature distilled water was sprayed until the emission intensity became stable. In this case, 30 seconds was sufficient. Spraying the sample again and measuring the emission intensity were repeated 10 times. FIG. 1 shows the results of the measurement converted to concentrations.

Next, the same sample was measured using distilled water heated at 60 ° C. instead of distilled water at room temperature under the same conditions. FIG. 2 shows the result of the measurement converted to a concentration. As can be seen from the results, when room temperature distilled water was used, the spraying state of the sample fluctuated due to the precipitation of salt in the atomization section of the nebulizer, and the measured value gradually increased. A measurement error of ± 1% or more has already occurred in the fourth measurement, and an error of as much as 5% has occurred in the tenth measurement. On the other hand, when the distilled water heated at 60 ° C. was used, all the measured values were within ± 1%, indicating that precise measurement could be continuously performed.

Comparative Test 2 The amount of lead in lead oxide-based ceramics was determined by the following two methods. Na ₂ CO ₃ : 0.12 g, H ₃ BO ₃ : 0.
03 g of 1.8% hydrochloric acid: dissolved in 100 ml.
A sample solution was prepared by adding 0 ppm of PbO. Use a cross-flow nebulizer and measure the wavelength 220.35
The emission intensity of lead was measured according to the procedure in nm. Thereafter, room temperature distilled water was sprayed until the emission intensity became stable. In this case, 30 seconds was sufficient. Spraying the sample again and measuring the emission intensity were repeated 10 times.
FIG. 3 shows the result of the measurement converted to a concentration.

Next, the same sample was measured using distilled water heated at 60 ° C. instead of distilled water at room temperature under the same other conditions. FIG. 4 shows the measurement results converted to concentrations. As can be seen from the results, when room temperature distilled water was used, the spraying state of the sample fluctuated due to the precipitation of salt in the atomization section of the nebulizer, and the measured value gradually increased. In the third measurement, the measurement error has already become ± 1% or more, and in the tenth measurement, an error of 8.6% has occurred. In contrast, 60
When using distilled water heated at ℃, all measured values are ± 1
%, Which indicates that precise measurement can be continuously performed.

Comparative Test 3 The determination of zirconium in alumina was performed by the following two methods. 3.6 g of 1 g of Li ₂ B ₄ O _{7 and} 1 g of oxalic acid
% Hydrochloric acid: dissolved in 100 ml, 1.00 ppm Zr
O ₂ was added to prepare a sample solution. Using a cross-flow nebulizer, the emission intensity of zirconium was measured at a measurement wavelength of 257.14 nm according to the procedure. Thereafter, room temperature distilled water was sprayed until the emission intensity became stable. In this case, 30 seconds was sufficient. Spraying the sample again and measuring the emission intensity were repeated 10 times.
FIG. 5 shows the result of the measurement converted to a concentration.

Next, the same sample was measured using distilled water heated at 60 ° C. instead of distilled water at room temperature, and the other conditions were the same. FIG. 6 shows the result of the measurement converted to a concentration. As can be seen from the results, when distilled water at room temperature was used, the spray state of the sample fluctuated due to the precipitation of salt in the atomization section of the nebulizer, and the measured values gradually increased with large fluctuations. The measurement error has already become ± 1% or more in the second measurement, and an error of 17% has occurred in the fifth measurement.
On the other hand, when the distilled water heated at 60 ° C. was used, the measurement was within ± 1% until the ninth measurement, and continuous measurement was possible within a practically acceptable range.

Comparative Test 4 The determination of zirconium in alumina was performed by the following two methods. Na ₂ CO ₃ : 0.12 g, H ₃ BO ₃ : 0.0
3 g of 1.8% hydrochloric acid: dissolved in 100 ml,
A sample solution was prepared by adding ppm of ZrO ₂ . Using a coaxial nebulizer, the emission intensity of zirconium was measured at a measurement wavelength of 257.14 nm according to the procedure. Thereafter, room temperature distilled water was sprayed until the emission intensity became stable. In this case, 30 seconds was sufficient. Spraying the sample again and measuring the emission intensity were repeated 10 times.
FIG. 7 shows the results of the measurement converted to concentrations.

Next, the same sample was measured using distilled water heated at 60 ° C. instead of distilled water at room temperature under the same conditions. FIG. 8 shows the result of the measurement converted to a concentration. As can be seen from the results, when room temperature distilled water was used, the spraying state of the sample fluctuated due to the precipitation of salt in the atomization section of the nebulizer, and the measured value gradually increased. In the third measurement, the measurement error has already become ± 1% or more, and in the tenth measurement, an error of as much as 24% has occurred. 60 ° C
When heated distilled water was used, most of the measured values were ± 1.
%, Which indicates that precise measurement can be continuously performed.

Comparative Test 5 Next, 100.0 ppm of Y ₂ was added to each of the high concentration salt solutions al.
Add O ₃ and use a cross-flow nebulizer to
As in Comparative Tests 1, 2, and 3, the temperature of distilled water sprayed between the samples was changed to compare the measurement conditions of the yttrium concentration. The results are shown in Table 1 below.

[0022]

[Table 1]

The composition of each sample solution is as follows. (A) Na ₂ CO ₃ : 2 g + 3.6% HCl: 100 ml (b) NaOH: 2 g + 3.6% HCl: 100 ml (c) K ₂ S ₂ O ₇ : 2 g + distilled water 100 ml (d) Na ₂ SO ₄ : 2 g + 100 ml of distilled water (e) Na ₂ O ₂ : 2 g + 3.6% HCl: 100 ml (f) Li ₂ B ₄ O ₇ : 2 g + 3.6% HCl: 100
Milliliter (g) Li ₂ BO ₇ : 2 g + 3.6% HCl: 100 ml (h) H ₃ BO ₃ : 4 g + distilled water 100 ml (i) Oxalic acid: 4 g + distilled water 100 ml (j) Tartaric acid: 4 g + distilled water 100 Milliliter (k) Al: 2 g + 7.2% HCl: 100 ml (l) Na ₂ CO ₃ : 1.5 g + H ₃ BO ₃ : 1.0 g
+ 1.8% HCl: 100 ml In Example 5, the measurement was repeated by spraying warm water at 30 ° C. alternately with the sample solution.

In Example 6, the measurement was repeated by alternately spraying the sample solution with warm water at 60 ° C. In Example 7,
The measurement was repeated by spraying 70 ° C. warm water alternately with the sample solution. In Example 8, the measurement was repeated by spraying a solution of 100 ml of warm water at 60 ° C. + a surfactant of 1 ml alternately with the sample solution. Triton X100 manufactured by Katayama Chemical Co., Ltd. was used as the surfactant.

In Comparative Example 5, these sample solutions were sprayed alternately with room temperature water as in the past, and repeated measurements were made. In Comparative Example 6, these sample solutions were alternately sprayed with room temperature water as usual, and the measurement was repeated by humidifying the argon gas. As a result of repeated measurement, error of concentration measurement value ±
When the number of times of continuous measurement within 1% is 6 or more times, there is no problem at all. ○, 1 to 5 times at practically no problem, Δ If it is possible, it is marked as x.

When room temperature water is sprayed as in the past, salt precipitation was remarkable in the atomization section of the nebulizer in samples f, g, h, i, j, and l, so that highly reliable measurement was impossible. there were. Also, when the argon gas was humidified, some effects were observed, but the effects were not sufficient for the samples h, i, and l. On the other hand, when the warming water at 30 ° C. is used, all the samples can be precisely measured at a level that does not cause a practical problem. Accurate measurement could be performed continuously six times or more with no error within ± 1%.

The same effect was obtained when a surfactant was added to 60 ° C. warm water. Similarly to Comparative Test 6 , 100.0 ppm of Y was added to each of the high concentration salt solutions m and n.
₂ O ₃ was added, and various acids were added to warm water sprayed between samples and used, and the measurement state of the yttrium concentration was compared with the case where no acid was added. The results are shown in Table 2 below.

[0028]

[Table 2]

The composition of each sample solution is as follows. (M) Nb: 0.5 g + 18% HCl: 100 ml (n) W: 0.5 g + tartaric acid: 1 g + 1.8% HCl:
100 ml In Example 6, these sample solutions were alternately sprayed with only 60 ° C. heated water to repeatedly measure.

In Example 9, the measurement was repeated by spraying a solution of 100 ml of warm water at 60 ° C. + 1 ml of 36% HCl alternately with the sample solution. In Example 10, the sample solution and the heating water were alternately heated at 60 ° C .: 100 ml: 61% HN.
O ₃ : One milliliter of the solution was sprayed for repeated measurements. In Example 11, heated water at 60 ° C. alternately with the sample solution:
The measurement was repeated by spraying a solution of 100 ml + 98% H ₂ SO ₄ : 1 ml.

In Example 12, the temperature was changed to 60 ° C. alternately with the sample solution.
The measurement was repeated by spraying a solution of 100 ml of warm water + 1 g of citric acid. Table 1 shows the notation method of measurement results.
Is the same as The measurement at a practically acceptable level is possible even when 60 ° C. heated water is used for the samples m and n, but more favorable results were obtained by adding an acid.

In the method of the present invention, the effect of a decrease in accuracy due to a change in the spraying efficiency was not observed even though the heating water was sprayed alternately with the sample solution. The reason for this is that the temperature in the chamber returns to room temperature again during the preliminary spraying of the sample solution after the completion of the spraying of the heated water, so that a stable spraying efficiency is obtained when actually performing the measurement. It is thought to be. FIG. 9A schematically shows a temperature change in the chamber when the sample solution and the heated water are sprayed alternately. That is, the temperature at the time of measurement is kept constant, and at the time of cleaning the atomization part of the nebulizer, the cleaning effect is enhanced by the heated water, so that highly accurate measurement is possible.

Next, an example of a cross-flow type nebulizer used in the method for measuring a solution sample of the present invention is shown in FIG. This cross-flow type nebulizer 10 includes a nebulizer main body 11.
And a chamber 12. The nebulizer main body 11 has a carrier gas inlet 13 for introducing a carrier gas such as an argon gas and a sample solution inlet 14 for introducing a sample solution, room temperature water, heated water and the like. Nebulizer atomization unit 18
Then, the sample, room temperature water, heated water, and the like enter the inside of the chamber 12 from the downstream end of the sample solution inlet 14 due to the negative pressure generated by the flow rate of the carrier gas introduced from the downstream end of the carrier gas inlet 13. It is being sucked out. The atomized sample particles in the chamber 12 have only an outlet 1 in which only relatively small particles are connected to the analysis unit.
Sent from 6. Particles having a relatively large particle diameter are discharged from the drain 17 to the outside.

Next, an example of a supply device for selectively supplying a sample to be supplied to the nebulizer 11 and room temperature water or heated water is shown in FIGS. To the sample solution inlet 14 of the nebulizer 11, a sample or room temperature water or heated water selectively sucked up by the suction nozzle control unit 21 is supplied by a suction pump 22. The siphoning nozzle control unit 21 sucks up the sample from the sample test tube 25 which is fitted in a large number of holes opened along the circumference in the vicinity of the outer periphery of the rotatable sample stage 23 by using the sample siphoning nozzle 26 or when room temperature water is discharged. A sample sucking nozzle 26 selectively sucks room-temperature water or heated water from the stored room-temperature water washing tank 27 or the heated-water washing tank 28 that stores heated water. Room temperature water is supplied from a room temperature water supply tank 30 to a room temperature water washing tank 27 by a room temperature water supply pump 31. Further, the heated water washing tank 28 is supplied with heated water from a heated water supply tank 32 provided with a heating section for heating the heated water by a heated water supply pump 33. Then, the sample suction nozzle 26 of the suction nozzle control unit 21 is rotatable as shown in FIG. 14, and the sample, the room temperature water, or the heated water is supplied from the test tube 25, the room temperature water washing tank 27, or the heated water washing tank 28. It is designed to selectively suck up. The sucked sample, room temperature water or heated water is supplied from the suction pump 22 to the sample solution inlet 14 of the nebulizer 10.
And supplied into the chamber 12.

In another embodiment, the room temperature or warm water may comprise a mixture of one or more inorganic acids, organic acids or surfactants. The sample stage 23 is driven by a drive shaft 36 as shown in FIG.
Are repeatedly rotated and stopped in the direction of arrow A shown in FIG. 3, and the sample in the sample test tube 25 is sequentially rotated one by one by the sample suction nozzle 26 to a position where it can be sucked up.

According to the supply device for selectively supplying the sample and room temperature water or heated water, the suction nozzle control unit 2
The sample, room temperature water, or heated water can be selectively sucked up by the rotatable sample sucking nozzle 26 provided in 1. Thereby, the sample, room temperature water or heated water is automatically drawn from the sample suction nozzle 26 to the nozzle control unit 21.
Therefore, the sample, room temperature water or heated water can be selectively supplied to the nebulizer 18 of the nebulizer automatically and easily by switching.

FIG. 12 shows an example of a coaxial nebulizer widely used similarly to the cross flow type. The coaxial nebulizer 40 includes a nebulizer main body 41 and a chamber 4.
Consists of two. The nebulizer body 41 has a carrier gas inlet 43 for introducing a carrier gas such as argon gas and a sample solution inlet 4 for introducing a sample solution, room temperature water, heated water, and the like.
4 is provided. In the nebulizing section 48 of the nebulizer, the sample solution inlet 44 is formed by a negative pressure generated by the flow rate of the carrier gas introduced from the downstream end of the carrier gas inlet 43.
A sample, room temperature water, heated water, and the like are sucked into the chamber 42 from the downstream end of the chamber 42. As for the atomized sample particles in the chamber 42, only particles having a relatively small particle size are sent out from an outlet 46 leading to the analysis unit. Particles having a relatively large particle diameter are discharged from the drain 47 to the outside.

FIG. 13 shows an example of an ultrasonic nebulizer widely used similarly to the cross flow type. The ultrasonic nebulizer 50 includes a transducer 51, an aerosol chamber 52, a heating tube 61, and a condenser 62.
Consists of The aerosol chamber 52 has a carrier gas inlet 53 for introducing a carrier gas such as argon gas and a sample solution inlet 54 for introducing a sample solution, room temperature water, heated water and the like. In the nebulizing part 58 of the nebulizer, the sample, room temperature water, heated water and the like injected from the sample injection port 54 are atomized by the vibration of the transducer 51. As for the atomized sample particles in the aerosol chamber 52, only particles having a relatively small particle size are sent out into the heating tube 61. The sample solution that has not been atomized and the sample particles having a relatively large particle size are discharged to the outside from a drain 57 provided in the aerosol chamber 52. The particles having a relatively small particle size are superheated in the heating tube 61 and then condensed in the condenser 62. When condensed, only relatively small particles are pumped out of the outlet 56 leading to the analyzer. Particles having a relatively large particle diameter are discharged from the drain 67 to the outside.

In the above-described embodiment, both the sample solution and the heated water are supplied from the sample solution inlet, but a method in which a heated water spray port is provided separately from the sample solution inlet can also be used. 16 to 18 show partial cross-sectional views of a nebulizer provided with a heated water spray port. Heating water spray port 19, 4
From 9 and 59, the nebulizer atomizing units 18 and 4
Warming water is sprayed on 8,58.

FIG. 19 shows an example in which a heating water spray port is provided in the supply device for selectively supplying the sample solution, room temperature water, and heating water shown in FIG. The heated water in the heated water supply tank 70 is supplied to the heated water spray port 19 by the heated water supply pump 71.

[Brief description of the drawings]

FIG. 1 is a diagram showing data on the relationship between the number of measurements and a measurement result in Comparative Example 1.

FIG. 2 is a diagram showing data on the relationship between the number of measurements and a measurement result in Example 1.

FIG. 3 is a diagram showing data on the relationship between the number of measurements and the measurement results in Comparative Example 2.

FIG. 4 is a diagram showing data on the relationship between the number of measurements and a measurement result in Example 2.

FIG. 5 is a diagram showing data on the relationship between the number of measurements and measurement results in Comparative Example 3.

FIG. 6 is a diagram showing data on the relationship between the number of measurements and a measurement result in Example 3.

FIG. 7 is a diagram showing data on the relationship between the number of measurements and the measurement results in Comparative Example 4.

FIG. 8 is a diagram showing data on the relationship between the number of measurements and the measurement result in Example 4.

9A is a diagram showing a relationship between each measurement time and a temperature in a chamber, and FIG. 9B is a diagram showing a relationship between each measurement time and a light emission intensity.

FIG. 10 is a flowchart illustrating a procedure of a measurement method according to an embodiment of the present invention.

FIG. 11 is a partial cross-sectional view showing a cross-flow type nebulizer used in an embodiment of the present invention.

FIG. 12 is a partial sectional view showing a coaxial nebulizer used in the embodiment of the present invention.

FIG. 13 is a partial sectional view showing an ultrasonic nebulizer.

FIG. 14 is a schematic side view showing a supply device for selectively supplying a sample solution, room temperature water, and heated water used in an example of the present invention.

FIG. 15 is a schematic plan view showing a supply device for selectively supplying a sample solution, room temperature water, and heated water used in an example of the present invention.

FIG. 16 is a partial sectional view showing a cross-flow type nebulizer provided with a heated water spray port.

FIG. 17 is a partial sectional view showing a coaxial nebulizer provided with a heated water spray port.

FIG. 18 is a partial sectional view showing an ultrasonic nebulizer provided with a heated water spray port.

FIG. 19 is a schematic plan view showing a supply device provided with a heated water spray port for selectively supplying a sample solution, room temperature water, and heated water.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 10 Nebulizer 11 Nebulizer 12 Chamber 18 Nebulizer atomization part 21 Suction nozzle control part 22 Suction pump 23 Sample stand 25 Sample test tube 27 Room temperature water washing tank 28 Heated water washing tank 35 Auto sampler

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-63-47638 (JP, A) JP-A-63-225150 (JP, A) JP-A-61-225637 (JP, A) JP-A-63-225637 168538 (JP, A) JP-A-2-64438 (JP, A) JP-A-4-64754 (JP, U) (58) Fields investigated (Int. Cl. ⁷ , DB name) G01N 21/62-21 / 74 G01N 27/62 G01N 1/00-1/34 JICST file (JOIS)

Claims (10)

(57) [Claims] 1. A method for measuring a solution sample, comprising: using a analyzer having a nebulizer for atomizing a sample solution, wherein heating water is supplied to an atomizing section of the nebulizer. 2. The method for measuring a solution sample according to claim 1, wherein the analyzer is one of a high frequency inductively coupled plasma emission spectrometer and a high frequency inductively coupled plasma mass spectrometer. 3. The method for measuring a solution sample according to claim 1, wherein the solution sample and the heated water are sprayed alternately. 4. The nebulizer according to claim 1, wherein heated water introduced from the outside is forcibly sprayed onto the atomizing part of the nebulizer.
Or the method for measuring a solution sample according to 2. And spraying 5. solution sample, according to claim 1, characterized in that alternately perform O by blowing pressurized hot water while being sprayed with water at room temperature, a solution sample according to any one of the 4 Measurement method. 6. The time for passing or blowing heated water to the atomizing part of the nebulizer is equal to or longer than the time required for the emission intensity or ionic intensity to change and stabilize by switching from the solution sample to the heated water. The method for measuring a solution sample according to claim 1, 2, 3, 4, or 5, wherein Claim temperature of 7. The pressurized hot water is characterized in that in the range of 30 ° C. above the boiling point or less, five or
Or the method for measuring a solution sample according to 6 . Is 8. A pressurized hot water, pressurized hot water alone, or claim 1,2,3,4,5,6, characterized in that it comprises an inorganic acid, one or more of a mixture of an organic acid or surfactant Also
Is a method for measuring a solution sample according to 7 . 9. A sample or heated water supply apparatus for performing the method for measuring a solution sample according to claim 1, comprising: a sample supply section for supplying a sample; a heated water tank for storing heated water; A suction nozzle that can be selectively immersed in a sample or heated water in the sample supply unit or the heated water tank; and a suction pump that selectively sucks up the sample or heated water from the suction nozzle and supplies the sample or heated water to the atomizing unit of the nebulizer. A sample or heated water supply device provided with 10. The sample or heated water supply apparatus according to claim 9 , wherein the sample supply unit has a rotatable turntable and a test tube in which a solution sample is placed and which is detachable from the turntable.