JP2000123784A - Quadrupole mass spectrometer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a small, simple mass spectrometer that has high resolution and is used to analyze a solution sample and used as an isotopic ratio monitor. SOLUTION: This mass spectrometer is provided with multiple quadrupole electrodes 6a to f and detectors 7-a to f of the same number as the quadrupole electrodes 6a to f which are arranged corresponding to the electrodes in a one-to-one form in a vacuum chamber 1, and one or more ion sources 4-1 to 5 which are arranged on the wall of the vacuum chamber 1 and introduce a liquid or gas sample into the vacuum chamber 1 from the atmosphere to ionize it. The respective quadrupole electrodes 6-a to f are arranged generally in parallel with one another and are so set as to pass specific ions, and the respective detectors 7-a to f detect the passed ions.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a quadrupole mass spectrometer, and more particularly to a small quadrupole mass spectrometer which can be easily used as a monitor.

[0002]

2. Description of the Related Art A quadrupole mass spectrometer includes + (U + Vcosω) between two pairs of opposing rods of a quadrupole electrode arranged in parallel in a vacuum chamber (this is called a quadrupole electrode).
t) and-(U + Vcosωt) (here,
U is a DC voltage component, and Vcosωt is a high-frequency AC voltage), by changing U, V or ω,
The mass spectrum is measured by changing the number of masses / charges that can stably pass through the quadrupole electrode.

In general, in a high-sensitivity mass spectrometer used for detailed identification or quantitative analysis, one set of quadrupole electrodes is arranged in a vacuum chamber, or a plurality of sets of quadrupole electrodes are connected in series. Due to the arrangement, ions must be converged to a specific position and introduced into the quadrupole electrode. Therefore, it is necessary to arrange a complicated ion optical system in front of the quadrupole electrode. .

[0004] Therefore, since the inside of the vacuum chamber must be kept at a high vacuum, the mass spectrometer becomes large and the handling is complicated. In addition, when mass spectrometry of isotope ions of a specific substance and determination of the isotope ratio require a practical high resolution, the magnetic field type mass spectrometer having the high resolution is very large. The device was used.

[0005] Further, a quadrupole mass spectrometer array in which a plurality of quadrupole electrodes are miniaturized and arranged and a gas sensor using the quadrupole mass spectrometer array are disclosed in US Pat.
193 and 5,401,962. Further, as a conventional technique for converting sample molecules in a solution into gaseous ions, an ion spray method (Analytica) is used.
l Chemistry, Vol. 59 (1987) No. 2
642 to 2646), electrospray method (Jonalof Physical Chemistr)
y, Vol. 88 (1984), pp. 4451-445.
9), atmospheric pressure chemical ionization (Analytical)
Chemistry, Vol. 54 (1982), No. 14
3 to 146).

[0006] Recently, as another ionization method different from the above-mentioned method, a sonic spray method in which ions are efficiently generated only by spraying a sample solution with a sonic gas has been reported. For example, Analytical Chemistr
y, vol. 66, pp 4457-4559 (19
94) or Analytical Chemist
ry, vol. 67, pp2878-2882 (1
995) or JP-A-7-306193 and JP-A-8-62200. In this method, it is considered that fine charged droplets are generated by the flow of the gas at the speed of sound, and the solvent molecules are separated to generate ions.

[0007]

As described above, the conventional mass spectrometer has high sensitivity, but is large and complicated to handle, and cannot be used as a simple monitor. Also, because a complex ion optical system is arranged inside,
There is a problem that it takes time to clean the inside of the vacuum chamber. When the isotope analysis is performed, there is a problem that an even larger and more complicated magnetic field type high resolution mass spectrometer is required. Further, the conventional small mass spectrometer array has no ion source for converting a solution sample into gaseous ions, so that it is used for analyzing only gas, and there is a problem that solution sample cannot be analyzed.

The present invention has been made in order to solve the problems of the prior art, and can mass-analyze a sample in a solution, omit an ion optical system, and easily clean the inside of a vacuum chamber. A quadrupole electrode mass spectrometer that can be used as a small, easy-to-handle monitor and miniaturized quadrupole electrodes to increase the resolution of mass spectrometry and easily measure the isotope ratio of substances The purpose is to provide.

[0009]

The structure of the quadrupole electrode mass spectrometer according to the present invention is as follows: a vacuum chamber wall is provided with fine droplets, vaporized or ions on the vacuum chamber surface from the atmosphere into the vacuum chamber; One or a plurality of pores for taking any sample in the shape of a circle and a rod arranged substantially in parallel and opposed to each other in the vacuum chamber are connected to each other so that a DC having a specific mass / charge number is passed therethrough. A plurality of quadrupole electrodes to which either a positive voltage or a negative voltage obtained by superimposing a voltage and a high-frequency AC voltage are applied, and the same number as the plurality of quadrupole electrodes and coaxial with the quadrupole electrodes. And a detector disposed in the above. Another configuration of the quadrupole electrode mass spectrometer according to the present invention includes a film on a wall of a vacuum chamber for taking a sample in the form of fine droplets or vaporized or ionic from the air into the vacuum chamber, A positive or negative voltage, which is obtained by superimposing a DC voltage and a high-frequency AC voltage so as to pass ions of a specific mass / charge number by connecting rods that are arranged in parallel and facing each other in a vacuum chamber, is formed. A plurality of applied quadrupole electrodes, and the same number of the quadrupole electrodes and detectors arranged coaxially in correspondence with the quadrupole electrodes, are provided. Things.

[0010] Still another configuration of the quadrupole electrode mass spectrometer according to the present invention comprises one or a plurality of ion sources for taking a liquid or gas sample from the atmosphere into the vacuum chamber and ionizing the vacuum chamber wall, and the vacuum chamber. A DC voltage and a high-frequency AC voltage are superimposed on each other so as to pass ions of a specific mass / charge number by connecting rods which are arranged substantially in parallel and facing each other. A plurality of quadrupole electrodes, and the same number of the plurality of quadrupole electrodes and detectors arranged coaxially opposite the quadrupole electrodes, is there.

[0011] Still another configuration of the quadrupole electrode mass spectrometer according to the present invention comprises one or more ion sources for taking a liquid or gas sample from the atmosphere into the vacuum chamber and ionizing the same on the wall of the vacuum chamber. A positive or negative voltage obtained by superimposing a DC voltage and a high-frequency AC voltage is connected to rods that are arranged in parallel in vacuum chamber and that oppose each other, so that ions having a specific mass / charge number pass through. A plurality of applied quadrupole electrodes, the same number of the plurality of quadrupole electrodes, and detectors provided on the same axis as the quadrupole electrodes, and one end of each of the detectors via the ion source. A plurality of capillaries for inserting the tip into the vacuum chamber and immersing the other end in each solution sample, sucking the solution sample by the pressure difference between the both ends, and introducing the solution sample into the ion source. Is characterized by

In any of the above quadrupole mass spectrometers, a flow path connecting the atmosphere to the vacuum chamber, a capillary inserted into the flow path to the inside of the vacuum chamber, and a tip outer diameter portion of the capillary And an orifice provided on the wall surface of the vacuum chamber having the inner diameter of the flow path, and ionization means for spraying and ionizing the solution sample in the capillary by an air flow flowing from the atmosphere into the vacuum chamber through the flow path. And
It is characterized by having. Further, in any one of the quadrupole mass spectrometers described above, heating means provided in the ion source, and introducing means for vaporizing the solution in the capillary by the heating means and introducing the solution into the vacuum chamber, It is characterized by having.

Further, in any one of the above-described quadrupole mass spectrometers, a needle electrode provided in the vacuum chamber is provided. Further, in any of the above quadrupole mass spectrometers, a plurality of accelerating electrode plates provided in the vacuum chamber, the ions are accelerated by the plurality of accelerating electrode plates, the axial direction of each quadrupole electrode And an incidence means for causing the light to enter.

Further, in any one of the above quadrupole mass spectrometers, a plurality of ions for detecting the same mass / charge number among the ions having a plurality of mass / charge numbers specified by the quadrupole electrode. An adder for adding the detection signal of the detector and an output unit for outputting a result value of the adder are provided. Furthermore, the quadrupole mass spectrometer described above further comprises an output unit that calculates an output value from the adder and outputs a mass / charge number for each quadrupole electrode. Is what you do. Furthermore, in any of the above quadrupole mass spectrometers,
It is characterized by comprising setting means for setting the specific mass / charge number of the plurality of quadrupole electrodes to the mass / charge number of a plurality of isotopes of the specific substance. Still further, in any of the above quadrupole mass spectrometers, the quadrupole electrode is miniaturized and operated in a low-vacuum vacuum chamber. Still further, in any of the above quadrupole mass spectrometers, a part of the vacuum chamber can be removed.

The quadrupole mass spectrometer having the above configuration will be functionally described. The quadrupole mass spectrometer reduces the size of the quadrupole electrode, specifies the applied voltage of the quadrupole electrode, and reduces the size of the applied power supply unit, thereby reducing the size of the vacuum chamber and increasing the resolution. , For isotope analysis. In addition, since the vacuum chamber can be made smaller by reducing the size of the quadrupole electrode, a vacuum pump having a high pumping capacity is not required, and the operation is simplified, and the vacuum chamber can be easily cleaned. In addition, in order to maintain high sensitivity, the quadrupole mass spectrometer converges ions with an ion optical system and efficiently introduces ions into the quadrupole electrode, so if the ion optical system is omitted, In order to maintain the function, a plurality of quadrupole electrodes are installed in parallel. In addition, the quadrupole mass spectrometer installed quadrupole electrodes corresponding to a plurality of types of ions corresponding to each isotope ion in parallel in order to measure the isotope ratio, and for each type of isotope, By adding the signal amounts measured by the quadrupole electrodes and calculating the sum, the isotope ratio can be monitored easily and efficiently. Further, the quadrupole mass spectrometer is installed with an ion source on the wall surface of the vacuum chamber and integrated with the quadrupole mass spectrometer, and the end of the capillary of the ion source is inserted into the vacuum chamber, By immersing the other end in the sample solution, the sample solution is sucked into the capillary little by little and introduced into the ion source by the pressure difference between both ends of the capillary, sprayed into the vacuum chamber and ionized. Therefore, a solution sample can also be analyzed.

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of a quadrupole mass spectrometer according to the present invention will be described with reference to FIGS. FIG. 1 is a schematic diagram of one embodiment of a quadrupole mass spectrometer according to the present invention, FIG. 2 is a schematic diagram of another embodiment of a quadrupole mass spectrometer according to the present invention, and FIG. Schematic diagram of one embodiment of the ion power supply unit of the quadrupole mass spectrometer according to the present invention, FIG. 4 is a schematic diagram of another embodiment of the ion power supply unit of the quadrupole mass spectrometer according to the present invention, FIG. 5 is a schematic view of still another embodiment of the ion power supply unit of the quadrupole mass spectrometer according to the present invention, and FIG. 6 is still another embodiment of the quadrupole mass spectrometer according to the present invention. FIG. 7 is a schematic view of still another embodiment of the quadrupole mass spectrometer according to the present invention. FIG. 8 is a schematic view of still another embodiment of the quadrupole mass spectrometer according to the present invention. FIG. 9 is a schematic view of still another embodiment of the quadrupole mass spectrometer according to the present invention,
FIG. 10 is a schematic diagram of one embodiment of an electrode arrangement of the quadrupole mass spectrometer according to the present invention, and FIG. 11 is a schematic diagram of another embodiment of the electrode arrangement of the quadrupole mass spectrometer according to the present invention. FIG. 12 is a schematic view of still another embodiment of the electrode arrangement of the quadrupole mass spectrometer according to the present invention, and FIG. 13 is still another embodiment of the electrode arrangement of the quadrupole mass spectrometer according to the present invention. FIG. 14 is a schematic view of another embodiment of the electrode arrangement of the quadrupole mass spectrometer according to the present invention, and FIG.
FIG. 4 is a schematic view of still another embodiment of the quadrupole mass spectrometer according to the present invention.

[Embodiment 1] In this embodiment, a mass spectrometer having two kinds of quadrupole electrodes corresponding to specific ions will be described. When only one kind of quadrupole electrode is provided, three or more kinds of quadrupole electrodes may be provided. In addition, the ion source and the pore are composed of five, and the quadrupole electrode and the detector are composed of six, but the ion source, the pore, the quadrupole electrode and the detector are arranged more than that. No problem. Although the numbers of the ion source and the quadrupole electrode are different in the present embodiment, they may be the same.

FIG. 1 shows an embodiment of a quadrupole mass spectrometer according to the present invention. In FIG. 1, the inside of a vacuum chamber 1 including an ion source 4-x, a quadrupole electrode 6-x, a detector 7-x, and the like is maintained at a vacuum by a vacuum pump 2. The vacuum pump 2 may be any of an oil rotary pump, a turbo molecular pump, an ion pump and the like. Since the degree of vacuum in the vacuum chamber 1 does not require a high degree of vacuum, a small pump having no high evacuation capacity may be used.

First, the sample introduction system will be described. The capillaries 3-1 to 5 pass through the inside of the ion sources 4-1 to -5 provided on the wall surface of the vacuum chamber 1 and the tip ends thereof correspond to the vacuum chamber 1
Has been introduced within. Since a pressure difference is generated at both ends of each of the capillaries 3-1 to 5, each of the capillaries 3-5
When the ends of the atmospheric pressure side of 1 to 5 are immersed in the solution, the solution is sucked little by little into the capillaries 3-1 to 5 and introduced into the ion sources 4-1 to 5 by the siphon action. become.

The solutions introduced into the ion sources 4-1 to -5 are:
The ions are sprayed into the vacuum chamber 1 to generate one or more types of ions 5. In the vacuum chamber 1, small quadrupole electrodes 6-a to 6-f are arranged. The quadrupole electrode 6-a,
For c and e, a DC voltage or a high-frequency AC voltage is applied to a quadrupole rod so as to stably pass ions 5 having a specific mass / charge number = Z.

Similarly, the quadrupole electrodes 6-b, d, and f are applied to the quadrupole rods so as to stably pass ions having a specific mass / charge number = Z ′ different from Z. Is applied with a DC voltage or a high-frequency AC voltage. Each ion 5 passing through each of the quadrupole electrodes 6-a to 6-f is detected by detectors 7-a to 7-f arranged one-to-one with respect to the quadrupole electrodes 6-a to 6-f. Is done. In the quadrupole mass spectrometer of this embodiment, only two types of ions are measured.

[Embodiment 2] Next, another embodiment of the quadrupole mass spectrometer according to the present invention will be described. The quadrupole mass spectrometer shown in FIG. 2 has many parts in common with the quadrupole mass spectrometer of FIG. 1, and the description of the common parts will be omitted because it is complicated, and the description will be focused on the characteristic parts. In FIG. 2, the same reference numerals as those in FIG. 1 denote corresponding members having the same configuration and function, and therefore, description thereof will be omitted.

FIG. 2 is a sectional view showing a case where an electrode plate 8 for accelerating ions is provided in the vacuum chamber 1 of the quadrupole mass spectrometer of the embodiment shown in FIG. The electrode plate 8 is disposed in close contact with the wall surface of the vacuum chamber 1, and the electrode plate 8 has a plurality of holes formed therein.
1 to 5 are inserted into the holes. The ion sources 4-1 to 5
And the electrode 8 may be insulated. Also,
The potential may be the same.

In the vacuum chamber 1, another electrode plate 9 is disposed at a position separated from the electrode plate 8, and the two electrode plates 8 and 9 are insulated from each other. The electrode plate 8,
9 is connected to the power supply 10 by the electric wire 11,
An acceleration voltage is applied between the electrode plates 8 and 9. The electrode plate 8,
During the period 9, either positive or negative ions are accelerated depending on the polarity of the acceleration voltage. Although not shown, a hole is formed in the electrode plate 9 to allow the accelerated ions 5 to pass therethrough. One or more small holes may be provided. Further, FIG. 2 shows a case where the electrode plate 8 is in close contact with the wall surface of the vacuum chamber 1, but may be installed separately.

In this case, since the electrode plate 8 is separated, the position of the hole formed in the electrode plate 8 is shifted, and the vicinity of the capillaries 3-1 to 5 on the axial extension is opened. It is preferable not to hinder the progress of the ions 5. Although FIG. 2 shows two electrode plates, three or more electrode plates may be provided.

Embodiment 3 Next, another embodiment of the quadrupole mass spectrometer according to the present invention will be described. In the present embodiment, various ion sources will be described. Except for the ion source of the quadrupole mass spectrometer shown in FIG. 3, since it is common to the quadrupole mass spectrometer of FIG. 1, the illustration and description of the common parts will be omitted because they are complicated. Will be described.

FIG. 3 is an enlarged schematic view of the ion source section when a sonic spray method is used as the ion source. In the ion source 4, a flow path 12 is formed so that air flows into the vacuum chamber 1 along the axial direction of the capillary 3, and an outlet of the flow path 12 to the vacuum chamber 1 has the flow path 12. The end of the capillary 3 in the solution flowing direction is inserted into the opening surface of the capillary 3, and the outer peripheral portion of the capillary 3 serves as a throttle. The orifice 13 is formed by the opening surface of the flow channel 12 and the capillary 3. .

In the orifice 13, the capillary 3
If the diameter of the orifice 13 is constant, the aperture ratio of the orifice 13 differs depending on whether or not the ratio of the area of the opening surface of the flow channel 12 to the area of the capillary 3 is almost the same. When the two area ratios are the same and close, the throttle ratio becomes small, and the pressure difference before and after the orifice 13 (generally, the upstream side of the throttle is called front) becomes small.

The air flows into the vacuum chamber 1 from the outer periphery of the capillary 3 due to a difference between the atmospheric pressure and the pressure in the vacuum chamber 1, and the solution in the capillary 3 is moved by the air flow. Is sprayed and the solution sample is ionized.
If the restricting ratio of the orifice is large, that is, if the restricting diameter is sufficiently small, the pressure difference before and after the orifice is large as described above, that is, a pressure loss occurs from the atmospheric pressure, and the pressure in the vacuum chamber 1 is substantially equal to the atmospheric pressure. There is no worry about rising to the same extent.

Further, another ion source will be described with reference to FIG. FIG. 4 is an enlarged sectional view of an ion source portion to which the sonic spray method of FIG. 3 is applied. Since the principle is the same as that of the sonic spray method in FIG. 3, the detailed description will not be repeated again and will be omitted, and differences will be described. In FIG. 4, the air flow flowing into the vacuum chamber 1 from the outer periphery of the capillary 3 is further laminar, so that the spray effect is further improved.

Still another ion source will be described with reference to FIG. FIG. 5 is an enlarged cross-sectional view of an ion source portion to which the heating spray method is applied as the ion source. A heater 14 is installed inside the ion source 4 to heat and spray the solution in the capillary 3. The heating of this solution further improves the spray effect.

[Embodiment 4] Next, referring to FIG.
Another embodiment of the quadrupole mass spectrometer according to the present invention will be described. The quadrupole mass spectrometer shown in FIG. 6 is substantially the same as the quadrupole mass spectrometer of FIG. 1 in principle, and the common parts are omitted because they are complicated. explain. In FIG. 6, the same reference numerals as those in FIG. 1 denote corresponding members having the same configuration and function, and thus description thereof will be omitted.

FIG. 6 shows the discharge needle electrode 15 in the vacuum chamber 1.
It is sectional drawing at the time of providing. In FIG. 6, a needle electrode 15 is disposed in the vacuum chamber 1, and a high voltage is applied to the needle electrode 15 to cause corona discharge. The corona discharge ionizes a non-ionized sample. Either positive ions or negative ions are generated according to the voltage polarity applied to the needle electrode 15. Also in this case, an electrode plate for acceleration may be provided.

[Embodiment 5] Next, referring to FIG.
Another embodiment of the quadrupole mass spectrometer according to the present invention will be described. The quadrupole mass spectrometer shown in FIG. 7 is substantially the same in principle as the quadrupole mass spectrometer shown in FIG. 1, and the common parts are omitted because they are complicated. explain. In FIG. 7, the same reference numerals as those in FIG. 1 denote corresponding members having the same configuration and function, and therefore, the description thereof will be omitted.

FIG. 7 is a cross-sectional view in a case where the ion sources 4-1 to 5 in FIG. 1 are omitted and the pores 16-1 to 16-5 are provided on the wall surface of the vacuum chamber 1. The embodiment shown in FIG. 7 is based on whether the solution sample is in the form of fine droplets in the atmosphere, or whether the solution sample is vaporized in the atmosphere into vapor or ions, or Is used in the case of gaseous state. Note that the needle electrode 15 need not be provided. Also in this case, the acceleration electrode plates 8 and 9 may be provided.

Embodiment 6 Next, referring to FIG.
Another embodiment of the quadrupole mass spectrometer according to the present invention will be described. The quadrupole mass spectrometer shown in FIG. 8 is substantially the same in principle as the quadrupole mass spectrometer shown in FIG. 1, and the common parts are omitted because they are complicated. explain. In FIG. 8, the same reference numerals as those in FIG. 1 denote corresponding members having the same configuration and function, so that the description thereof will be omitted.

FIG. 8 is a cross-sectional view in the case where the membrane 17 is arranged instead of the pores of FIG. In the embodiment of FIG. 8, as in the embodiment of FIG. 7, the sample solution is formed into fine droplets in the atmosphere, the sample solution is vaporized in the atmosphere into vapor, or the sample solution is It is used when it is ionized or the sample is gaseous. FIG.
As shown in the figure, a film 17 is disposed on the wall surface of the vacuum chamber 1, and the film 17 has a property of allowing droplets, vapors, ions, or gases in the air to pass therethrough and introduced into the vacuum chamber 1. ing. Further, a needle electrode 15 is arranged in the vacuum chamber 1,
By applying a high voltage to the needle electrode 15 to cause corona discharge, a non-ionized sample is ionized. It is to be noted that the needle electrode 15 functions without the need to be provided, and in this case, the acceleration electrode plates 8 and 9 may be provided.

Embodiment 7 Next, referring to FIG.
Another embodiment of the quadrupole mass spectrometer according to the present invention will be described. The quadrupole mass spectrometer shown in FIG. 9 has almost the same measurement principle as the quadrupole mass spectrometer shown in FIG. 1, and differs in the processing of data after the detector. Common parts will be omitted because they are complicated, and the description will focus on characteristic parts. In FIG. 9, the same reference numerals as those in FIG. 1 denote corresponding members having the same configuration and function, and therefore description thereof will be omitted.

The quadrupole mass spectrometer shown in FIG. 9 is a cross-section in which detectors corresponding to quadrupole electrodes for analyzing ions of the same type are connected by signal lines, and the detection signal amounts of the detectors are added. FIG. As shown in the figure, a detector 7 corresponding to the quadrupole electrodes 6-a, 6c, and e that allows ions of a specific mass / charge number = Z in the vacuum chamber 1 to pass stably among the quadrupole electrodes.
-A, c, and e are connected by the signal line 18-1.

Further, a quadrupole electrode 6 that allows ions having a specific mass / charge number = Z ′ different from Z to pass therethrough stably.
The detectors 7-b, d, and f corresponding to b, d, and f are connected by a signal line 18-2. The detectors 7-a, c,
The signals detected at e are added and sent to the arithmetic unit 19 via the signal line 18-1 to be added. Similarly, the signals detected by the detectors 7-b, d, and f are added and sent to the arithmetic unit 19 via the signal line 18-2, or sent to the arithmetic unit 19 via the signal line 18-2. Is added.

The signal value sent to the arithmetic unit 19 does not have to be the sum of the values of the detectors 7-a, c, e or 7-b, d, f. Another calculated value associated with the total amount of each detected value may be used. The calculation value corresponding to each ion amount is further calculated by the calculation unit 19 to calculate a value corresponding to the ion amount ratio or the ion amount difference. For example, when each ion is an isotope ion of a certain substance, an isotope ratio can be obtained. The quadrupole electrode is
When the size is reduced, the distance between the ion source and the detector is reduced and the resolution of mass separation is increased. Therefore, when measuring isotopes, it is desirable to use a smaller quadrupole electrode.

Next, a method of arranging small quadrupole electrodes in parallel used in the above embodiment will be described. FIG. 10 is a perspective view showing an example of small quadrupole electrodes arranged in parallel. 11 to 14 are cross-sectional views in a direction perpendicular to the quadrupole rods showing an arrangement when two types of quadrupole electrodes corresponding to two types of ions are arranged. A quadrupole electrode 6-a for passing ions having a mass / charge number Z and a quadrupole electrode 6-b for passing ions having a mass / charge number Z 'are alternately arranged. Since it is considered that the two types of ions are present in the vacuum chamber 1 almost equally, it is preferable to arrange the same number of ions alternately. The illustrated example is merely an example, and it may be arranged in another arrangement and may not be arranged in this way.

FIG. 15 is a block diagram of a solution sample monitoring system using the present quadrupole electrode mass spectrometer. The end of the capillary 3 is immersed in the solution sample 20. The sample 20 is sucked into the capillary 3 little by little, introduced into the ion source 4, ionized, and introduced into the vacuum chamber 1. The vacuum chamber 1 and the vacuum pump 2
Connected by A cable 22 in which a plurality of signal lines are bundled comes out of the vacuum chamber 1 and is connected to a personal computer 23. The personal computer 23 stores and calculates the signal value transmitted by the cable 22, and further displays the calculation result.

In each of the above embodiments, if the vacuum chamber 1 is configured so that a part of the wall surface can be removed, the inside can be easily cleaned, and the monitor can be conveniently used. Further, as described in detail above, the present quadrupole mass spectrometer is used for microanalysis such as environmental science and industrial analysis. In particular, the above system may be used, for example, for monitoring pollutants in waterworks. Absent. It is also effective for use in the analysis of stable isotopes, and is effective when used as a monitor for natural products, nuclear reaction products, stable isotope tracers, and as an isotope ratio monitor for water and alcohol.

[0045]

As described above in detail, according to the structure of the present invention, a sample in a solution can be subjected to mass spectrometry, the inside of a vacuum chamber can be easily cleaned, and it is small and easy to handle, and can be used as a monitor. Further, by reducing the size of the quadrupole electrode, it is possible to provide a quadrupole electrode mass spectrometer capable of increasing the resolution of mass spectrometry and easily measuring the isotope ratio of a substance.

[Brief description of the drawings]

FIG. 1 is a schematic view of an embodiment of a quadrupole mass spectrometer according to the present invention.

FIG. 2 is a schematic view of another embodiment of the quadrupole mass spectrometer according to the present invention.

FIG. 3 is a schematic diagram of an embodiment of an ion power supply unit of the quadrupole mass spectrometer according to the present invention.

FIG. 4 is a schematic diagram of another embodiment of the ion power supply unit of the quadrupole mass spectrometer according to the present invention.

FIG. 5 is a schematic diagram of still another embodiment of the ion power supply unit of the quadrupole mass spectrometer according to the present invention.

FIG. 6 is a schematic view of still another embodiment of the quadrupole mass spectrometer according to the present invention.

FIG. 7 is a schematic view of still another embodiment of the quadrupole mass spectrometer according to the present invention.

FIG. 8 is a schematic diagram of still another embodiment of the quadrupole mass spectrometer according to the present invention.

FIG. 9 is a schematic diagram of still another embodiment of the quadrupole mass spectrometer according to the present invention.

FIG. 10 is a schematic view of an embodiment of an electrode arrangement of the quadrupole mass spectrometer according to the present invention.

FIG. 11 is a schematic view of another embodiment of the electrode arrangement of the quadrupole mass spectrometer according to the present invention.

FIG. 12 is a schematic view of still another embodiment of the electrode arrangement of the quadrupole mass spectrometer according to the present invention.

FIG. 13 is a schematic view of still another embodiment of the electrode arrangement of the quadrupole mass spectrometer according to the present invention.

FIG. 14 is a schematic view of still another embodiment of the electrode arrangement of the quadrupole mass spectrometer according to the present invention.

FIG. 15 is a schematic view of still another embodiment of the quadrupole mass spectrometer according to the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Vacuum chamber, 2 ... Vacuum pump, 3, 3-1-5 ... Capillary, 4, 4-1-5 ... Ion source, 5 ... Ion, 6,
6-a to f: quadrupole electrode, 7, 7-a to f: detector, 8
... Electrode plate, 9 ... Electrode plate, 10 ... Power supply, 11 ... Electric wire, 1
2, ... flow path, 13 ... orifice, 14 ... heater, 15
... needle electrode, 16, 16-1 to 5 ... pore, 17 ... membrane, 18
-1 to 2 ... signal line, 19 ... arithmetic unit, 20 ... sample solution, 2
1 ... hose, 22 ... cable, 23 ... personal computer.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Izumi Waki Inventor 2520 Akanuma, Hatoyama-cho, Hiki-gun, Saitama F-term in Hitachi, Ltd. Basic Research Laboratories 5C038 EE01 EE02 EF03 EF04 JJ02 JJ06 JJ09

Claims (13)

[Claims] 1. One or a plurality of fine holes for taking a sample in the form of a fine droplet, a vapor, or an ion from the atmosphere into the vacuum chamber on the wall surface of the vacuum chamber, and substantially parallel to the vacuum chamber. A plurality of quadruples to which a positive or negative voltage obtained by superimposing a DC voltage and a high-frequency AC voltage so as to pass ions of a specific mass / charge number by connecting arranged and opposed rods are applied. A quadrupole mass spectrometer comprising: a pole electrode; and a plurality of detectors arranged in the same number as the plurality of quadrupole electrodes and coaxially corresponding to the quadrupole electrodes. 2. A film on a wall surface of a vacuum chamber for taking a sample in the form of a fine droplet, a vapor, or an ion from the atmosphere into the vacuum chamber, and a film arranged substantially in parallel and opposed to each other in the vacuum chamber. A plurality of quadrupole electrodes to which a positive or negative voltage is applied, in which a DC voltage and a high-frequency AC voltage are superimposed so as to pass ions of a specific mass / charge number, and A quadrupole mass spectrometer comprising: a plurality of quadrupole electrodes; and the number of detectors arranged coaxially in correspondence with the quadrupole electrodes. 3. One or more ion sources for taking a liquid or gas sample from the atmosphere into the vacuum chamber and ionizing them on the wall surface of the vacuum chamber, and connecting rods disposed in parallel and facing each other in the vacuum chamber. And a plurality of quadrupole electrodes to which a positive or negative voltage obtained by superimposing a DC voltage and a high-frequency AC voltage is applied so as to pass ions of a specific mass / charge number, A detector arranged in the same number as the number of the quadrupole electrodes and coaxially opposed to the quadrupole electrodes. 4. Connecting one or more ion sources for taking a liquid or gas sample from the atmosphere into the vacuum chamber and ionizing the same on the wall surface of the vacuum chamber, and connecting rods arranged substantially in parallel and facing each other in the vacuum chamber. And a plurality of quadrupole electrodes to which a positive or negative voltage obtained by superimposing a DC voltage and a high-frequency AC voltage is applied so as to pass ions of a specific mass / charge number, The same number of quadrupole electrodes, and a detector provided on the same axis as the quadrupole electrode, and one end is inserted into the vacuum chamber through the ion source, and the other end is inserted into the vacuum chamber. And a plurality of capillaries which are immersed in the solution sample described above, aspirate the solution sample by the pressure difference between the both ends, and introduce the capillary into the ion source. 5. The quadrupole mass spectrometer according to claim 3, wherein a flow path connecting the atmosphere and the vacuum chamber, a capillary inserted into the flow path to the inside of the vacuum chamber, A solution sample in the capillary is sprayed by an orifice provided on a wall surface in the vacuum chamber including an outer diameter portion of a tip of a capillary and an inner diameter of the flow path, and an air flow flowing from the atmosphere into the vacuum chamber through the flow path. A quadrupole mass spectrometer, comprising: ionization means for performing ionization. 6. The quadrupole mass spectrometer according to claim 3, wherein a heating unit provided in the ion source, and a solution in the capillary is vaporized by the heating unit to enter the vacuum chamber. A quadrupole mass spectrometer comprising: an introduction means for introducing. 7. The quadrupole mass spectrometer according to claim 5, wherein a needle electrode is provided in the vacuum chamber. 8. The quadrupole mass spectrometer according to claim 1, wherein a plurality of accelerating electrode plates provided in said vacuum chamber and ions are accelerated by said plurality of accelerating electrode plates. A quadrupole mass spectrometer, comprising: an incidence means for causing incidence in the axial direction of the quadrupole electrode. 9. The quadrupole mass spectrometer according to claim 1, wherein the same mass / charge number is detected from a plurality of mass / charge number ions specified by the quadrupole electrode. A quadrupole mass spectrometer, comprising: an adder that adds detection signals of a plurality of detectors to be performed; and an output unit that outputs a result value of the adder. 10. The quadrupole mass spectrometer according to claim 9, further comprising output means for calculating an output value from said adder and outputting a mass / charge number for each of said quadrupole electrodes. A quadrupole mass spectrometer. 11. The quadrupole mass spectrometer according to claim 9, wherein a specific mass / charge number of the plurality of quadrupole electrodes is determined by a mass / charge of a plurality of isotopes of a specific substance. A quadrupole mass spectrometer comprising a number setting unit. 12. The quadrupole mass spectrometer according to claim 1, wherein said quadrupole electrode is miniaturized and operated in a low-vacuum vacuum chamber. apparatus. 13. The quadrupole mass spectrometer according to claim 1, wherein a part of the vacuum chamber can be removed.