CN107464735A - A kind of new chlorine bromine isotope mass spectrometer and its analysis method - Google Patents
A kind of new chlorine bromine isotope mass spectrometer and its analysis method Download PDFInfo
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- CN107464735A CN107464735A CN201710510223.6A CN201710510223A CN107464735A CN 107464735 A CN107464735 A CN 107464735A CN 201710510223 A CN201710510223 A CN 201710510223A CN 107464735 A CN107464735 A CN 107464735A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
- G01N27/68—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode using electric discharge to ionise a gas
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/0027—Methods for using particle spectrometers
- H01J49/0031—Step by step routines describing the use of the apparatus
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/004—Combinations of spectrometers, tandem spectrometers, e.g. MS/MS, MSn
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/04—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components
- H01J49/0422—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components for gaseous samples
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/10—Ion sources; Ion guns
- H01J49/105—Ion sources; Ion guns using high-frequency excitation, e.g. microwave excitation, Inductively Coupled Plasma [ICP]
Abstract
The invention provides a kind of ion gun, including two reaction gas inlet ducts, is respectively arranged at the arrival end and the port of export for reacting ionization tube.New chlorine bromine isotope mass spectrometer is also disclosed, is coupled and formed with capillary gas chromatography system and magnetic substance spectra system by above-mentioned ion gun.And chlorine or bromine isotopic ratio analysis method is disclosed, sample reacts through radio frequency discharge and ionized under the auxiliary of reaction gas, and in the presence of reaction gas is supplemented, the chlorine or bromine in sample forms pure chlorine anion or bromine anion, so that quality analysis is used.The introducing and control that the present invention passes through reaction gas, under radio frequency discharge effect, obtain pure chlorine anion or bromine anion, the design and adjustment of partial magnetic field and faraday detector are composed by magnetic substance, form a kind of new chlorine bromine isotope mass spectrometer, analysis precision is high, and thoroughly solves the problems, such as the isobaric interference of conventional isotope test, can be applied to chemical industry, environmental protection, learn, the numerous areas such as medical science.
Description
Technical field
The present invention relates to a kind of ion gun, new chlorine bromine isotope mass spectrometer and chlorine or bromine isotopic ratio analysis method,
Belong to mass spectrometric analysis for isotope field.
Background technology
As geoscience, environmental science, Food Science and medical research are constantly goed deep into, traditional bulk sample product isotope
Ratio Analysis (BSIA) can not meet Research Requirements, and new organic monomer isotope technology (CSIA) turns into forward position
Study hotspot.CSIA methods can be used to identify and follow the trail of underground water, surface water and soil organic contamination source, monitor organic dirt
Contaminate the degradation process of thing and examine the effect of prophylactico-therapeutic measures, differentiate the production firm of chlorinatedorganic, investigate organic contamination event
The related responsibility of producer, identify the focus source of major disease etc. purposes.
With being on the increase for halo organic pollution, in CSIA technologies except traditional carbon (13C/12C), hydrogen (2H/1H)、
Oxygen (18O/16) etc. O outside stable isotope, chlorine (37Cl/35Cl), bromine (79Br/81Br) Stable isotope ratio analysis has become heat
Point.
It is current that to be used for testing chlorine bromine isotope common instrument be isotope ratio mass spectrum (IRMS), its ion gun used for
Electron impact ionization source (EI), the form of chips for ionizing to obtain are chloromethanes ion or bromomethane ion, magnetic core logical circuit deflection and farad
The mass number of the reception is 50,52 or 94,96 etc..Although this quasi-instrument can carry out chlorine bromine isotope in halogenated organic matters
Analysis, but method flow is extremely complex, it is necessary to which chlorinatedorganic is converted into chloromethanes (CH3Cl), then again by converted product
It is sent into mass spectrograph and is ionized into CH3Cl+, quality analysis and detection are then carried out again, because this conversion process is very tired in itself
Difficulty, therefore application is very limited, bromo organic matter is also same situation.
Thermal ionization mass spectrometry (tims) (TIMS) may also be used for analyzing chlorine bromine isotope, and its ionization source configured is hot surface ionization type
Ion gun, abbreviation thermal ionization source, its general principle are that the sample that will be prepared is coated in heated metal surface, and sample component exists
Lost in thermal evaporation process or obtain electronics and ionize.Although thermal ionization source has the advantages of ionizing efficiency is good, memory effect is low,
But organochlorine can only be converted into when testing chlorine or bromine isotope inorganic chlorine then again synthesizing chlorinated caesium can just be applied to
On sample band, this process is difficult to complete online.
Also a kind of mass spectrograph for being used for doing the analysis of chlorine bromine isotope is to increase high temperature combustion among gas-chromatography and mass spectrum
Burn device, halogenated organic matters from gas-chromatography separation after enter high-temp combustion device (HTC), more than 1300 degree at a high temperature of,
Organic matter is converted into the form of hydrogen chloride (HCl) or hydrogen bromide (HBr), is then ionized, deflects and detects, and ionization source is still
Using the electron impact ionization source (EI) of classics, Faraday cup detection quality number is (36,38) or (80,82).
The B of document CN 102590379 disclose a kind of based on the chlorine bromine isotope analysis instrument in negative chemical ionization source and side
Method, this method realize multiclass chloro or bromo organic matter by the adjustment of ion gun and the conversion of drainage pattern and are being ionized
Chlorine or bromine is set to be separated with carbon skeleton simultaneously, so as to reach analysis purpose by directly gathering (35,37) or (79,81).Should
Method can be in the case where ensureing analysis precision, Simplified analysis flow, improves analyze speed.But due to negative chemical ionization it is owned by France in
A kind of Soft ionization techniques, the efficiency of ionization source is not still high, and the stronger material of moieties structural symmetry (such as hexachloro-benzene) is still
Can not realize is peeled off halogen atom while ionization.
The invention discloses a kind of ion gun based on radio frequency discharge principle, by the introducing and control of reacting gas,
Under radio frequency discharge effect, pure chlorine anion or bromine anion is obtained, partial magnetic field and faraday detector are composed by magnetic substance
Design and adjustment, form a kind of new chlorine bromine isotope mass spectrometer, and develop its supporting analysis method.New instrument
Device full name is named as gas-chromatography-radio frequency discharge reactive ion source-isotope mass spectrometer (GC-RFRIS-IRMS).
The content of the invention
A kind of the present invention is intended to provide ion gun of high accuracy, high efficiency and strong applicability.
To realize goal of the invention, the invention provides a kind of ion gun, including reaction ionization tube, induction coil, power to put
Big device and radio-frequency signal generator, reaction ionization tube stage casing are induced coil and wrapped up, the radio-frequency signal generator and power
Amplifier is of coupled connections, the radiofrequency signal of radio-frequency signal generator is exaggerated by signal after power amplifier to be strengthened and transmits
Onto induction coil, radiofrequency signal field is internally formed in induction coil, it is characterised in that：Also include two reaction gas air inlets to fill
Put, be respectively arranged at the arrival end and the port of export of reaction ionization tube.The carrier gas distillated by gas-chromatography is connected with reaction ionization tube
And assisted reaction gas, the reaction gas inlet duct of gas-phase chromatographic capillary column end and arrival end pass through reducer union and reaction
Ionization tube connects, and is passed through respectively for carrier gas and first via assisted reaction gas, carrier gas and first via assisted reaction gas are in radio frequency
Electric discharge can be produced under effect so that gas ionization；Another reaction gas inlet duct is terminated with ion source outlet, can be passed through
Two road reacting gas, in the presence of the second road reacting gas, the gas after electric discharge ionization can obtain in the presence of crash response
Cooling to a certain extent, and ultimately form clean negatively charged object ion by dissociating resonating electron capture reaction
(i.e.35Cl-、37Cl-Or79Br-、81Br-).Two-way reaction gas introduces by mass flow controller.
Preferably, the reaction ionization tube is made up of high temperature resistant quartz ampoule or ceramic material.
Preferably, the radio frequency range of the radio-frequency signal generator is between 20-400MHz.
Present invention also offers a kind of high accuracy, high efficiency, can on-line measurement new chlorine bromine isotope mass spectrometer, by
Above-mentioned ion gun couples composition with capillary gas chromatography system and magnetic substance spectra system, the capillary gas chromatography system
The arrival end of the reaction ionization tube of capillary column and ion gun connects, and the port of export for reacting ionization tube connects with magnetic substance spectra system,
Wherein magnetic substance spectra system include ion transmission channel, magnetic substance contents analyzer, Faraday cup ion detection and signal output system and
Corresponding vacuum system.
Preferably, the capillary column length range of capillary gas chromatography system is between 30-60 rice, chromatographic column theory tower
Plate number is higher than 3000 every meter, and total number of plates is up to 105More than, the appearance time of different component is between 10-50s.
Preferably, the ion detection and segment signal output include Faraday cup detector and electron multiplier, farad
The glass of mass number received is (35,37) or (79,81), and the Faraday cup detector uses the arrangement of 3 Faraday cups, its
In a passage by switch share.
Wherein magnetic mass analysis part uses the magnetic field of 230mm radiuses, and magnetic field incident, outgoing border use 26.5 degree, its
Theoretical abbe number is 920, source slit 0.3mm, receives slit 1.4mm, and mass resolution is more than 160.
Present invention also offers it is a kind of based on above-mentioned isotope mass spectrometer realize chlorine or bromine isotopic ratio analysis method,
Specifically include following steps：
A, the sample by chlorine or bromine for organic matter, load gas chromatography system and separated；
B, the component after chromatography is directly flowed into the reaction ionization tube of ion gun by capillary column, and reaction gas is same
When from anti-
The arrival end of ionization tube is answered to import, object reacts through radio frequency discharge and ionized under the auxiliary of reaction gas, and supplement is anti-
Should gas
Imported from the port of export of reaction ionization tube, in the presence of reaction gas is supplemented, the chlorine or bromine in object forms pure
Net chlorine
Anion or bromine anion, so that quality analysis uses；
C, chlorine or bromine anion enters magnetic substance contents analyzer through ion transmission channel, by Faraday cup after being deflected in magnetic field
Ion
Detection and signal output system receive detection.
Preferably, the reaction gas is helium or argon gas, range of flow 1.0-50.0mL/min.
Preferably, the supplement reaction gas is nitrogen, range of flow 1.0-100.0mL/min.
The present invention uses the ion gun of innovative design, is ionized by the radio frequency with reaction controlling function sample is transformed
Journey is combined into one with ionization process, greatly reduces analysis process, passes through the magnetic mass of supporting adaptation ionization fragment requirement
The coupling of analyzer and Faraday detector forms a whole set of analytical instrument.Instrument is combined with gas-chromatography, a whole set of instrument of formation
Device is named as gas-chromatography radio frequency reaction ionised isotopes mass spectrum (GC-RFRIS-IRMS).Because this ionization mode can be direct
Obtain clean chlorine anion or bromine anion (i.e.35Cl-、37Cl-Or79Br-、81Br-), and overcome completely conventional method because
Ionize fragment in containing it is other it is hydrocarbon wait elements and caused by isobaric interference；Due to this ionization process discharge process energy
It is relatively strong, and the uninterrupted of different target thing regulation reaction gas can be directed to, it can be ensured by the regulation of first via reaction gas
The generation of discharge process, it can make the organic matter after ionization that dissociation resonating electron occur by the adjustment of the second road reaction gas and capture
Reaction, so as to advantageously form anion, because two-way reaction gas can be adjusted, therefore can realize whole halos in theory
The ionization of organic matter simultaneously makes chlorine atom or bromine atoms obtain peeling off so as to realize the analysis of its isotopic ratio；Used in this instrument
Reaction gas flow speed is smaller, typically smaller than 100mL/min, therefore also smaller to the vacuum-load of whole instrument, is advantageous to save instrument
Device cost simultaneously keeps stability of instrument.This principle of instrument is novel, design is exquisite, and not only analysis precision is high, and thoroughly solves
Isotope test isobaric interference problem, be a kind of mass-spectrometric technique of innovation, can be applied to chemical industry, environmental protection,
The numerous areas such as, medical science.
Brief description of the drawings
Fig. 1 is the ion source structure schematic diagram of the present invention；
Fig. 2 is the magnetic mass analysis part structural representation of the present invention；
Fig. 3 is the ion detection and segment signal output arrangement schematic diagram of the present invention；
Fig. 4 is the isotope mass spectrometer structural representation of the present invention.
Embodiment
The present invention is further described in detail with reference to embodiment, the embodiment provided is only for explaining
The bright present invention, and be not construed as limiting the scope of the present invention.
Embodiment 1
As shown in figure 4, this new chlorine bromine isotope mass spectrometer by capillary gas chromatography system 100 and ion gun 200 and
The coupling composition of magnetic substance spectra system 300, as shown in figure 1, the ion gun 200 includes reaction ionization tube 210, induction coil 220, work(
Rate amplifier 230 and radio-frequency signal generator 240, reaction ionization tube 210 stage casing are induced coil 220 and wrapped up, the radio frequency
Signal generator 240 is connected with power amplifier coupling 230, and the radiofrequency signal of radio-frequency signal generator 240 passes through power amplification
Signal, which is exaggerated, after device 230 strengthens and is transferred on induction coil 220, is internally formed radiofrequency signal field in induction coil, also wraps
Two reaction gas inlet ducts 250 are included, are respectively arranged at the arrival end and the port of export of reaction ionization tube.The capillary gas phase color
The arrival end for the reaction ionization tube 210 that the capillary column of spectra system passes through reducer union and ion gun connects, magnetic substance spectra system by
Ion hop 310, magnetic substance contents analyzer part 320 and Faraday cup ion detection and segment signal output 330 are formed, instead
Answer the port of export and ion hop 310, magnetic mass analysis part 320, ion detection and segment signal output of ionization tube 210
330 are sequentially connected.
The capillary column length range of capillary gas chromatography system 100 is between 30-60 rice, chromatographic column theoretical cam curve
Higher than 3000 every meter, total number of plates is up to 105More than, the appearance time of different component is between 10-50s.As shown in Fig. 2 magnetic substance
Measuring analysis part 320 includes source slit 321, magnetic field 322 and receives slit 323, magnetic field radius 230mm, magnetic field incident, outgoing side
Boundary uses 26.5 degree, and its theoretical abbe number is 920, source slit 0.3mm, receives slit 1.4mm, and mass resolution is more than 160；
As shown in figure 3, the ion detection and segment signal output 330 include Faraday cup detector and electron multiplier
332, the mass number that Faraday cup 331 is received is (35,37) or (79,81), and the Faraday cup detector uses 3 faraday
The arrangement of cup, one of passage are shared by switching.
Whole spectrometer system is in high vacuum state, is realized using multi-stage vacuum, from reducer union to Ion source pressure
Scope is from several pas to 10-3Pa, analysis conduit vacuum are higher than 10-4Pa。
Embodiment 2
The chlorine isotope ratio Analysis method of chlorinated hydrocarbon contaminants in underground water pollution place, instrument are institute of the present invention
The gas-chromatography radio frequency discharge reaction ionised isotopes mass spectrograph (GC-RFRIS-IRMS) stated, corollary equipment fill for purge and trap
(OI companies of the U.S., model 4660) is put, detection target is trichloro ethylene, is comprised the following steps：
A, water sample is loaded into purge and trap instrument and carries out purge and trap instrument, collecting trap is No. 10 traps, and purge gass are nitrogen, purging
Flow 40mL/min, purge time 11min；180 DEG C of parsing preheating, 190 DEG C of resolution temperature, parses time 0.5min；Bakee temperature
220 DEG C of degree, bakee time 6min；Realize the enrichment of chlorinatedorganic；
B, gas-chromatography separates：By the chlorinatedorganic sample after enrichment, load gas chromatography system and separated, gas phase
Chromatographic separation condition：Capillary chromatographic column is Rtx-624 (column length 30m, internal diameter 0.25mm, 0.25 μm of thickness), post beginning temperature 40
DEG C, keep 2min；With 20 DEG C/min temperature programmings to 210 DEG C, 5min is kept；Injector temperature：220℃；Split sampling, shunting
Than 20；Column flow rate 1mL/min；
C, the component after chromatography is directly flowed into the reaction ionization tube of ion gun by tubing string, through radio frequency discharge field
Ionization, radio frequency operation voltage 12V, working frequency 20MHz；Reaction gas helium gas flow 1.0mL/min, supplement reaction gas nitrogen flow
1.0mL/min, the chlorine in organic matter trichloro ethylene are ionized to form chlorine anion, while efficiently produce35Cl-、37Cl, for matter
Amount analysis uses；
D, caused by ionization35Cl-、37Cl-Deflect under the influence of a magnetic field, then by the reception matter of isotope mass spectrometry
The Faraday cup that number is 35,37 is measured to receive35Cl-、37Cl-, output is finally amplified by signal detector, receives detection
Detect35Cl-、37Cl-, respective peak intensity, I37, I35And isotopic ratio R is calculated by following formulaCl：
Finally by the R of above-mentioned result of calculationClValue calculates compared with the similar standard substance of known isotopic standard value,
Calculation formula is as follows：
WhereinFor standard substance value.
Embodiment 3
The bromine isotope analysis of decis in pedotheque, instrument are that gas-chromatography radio frequency of the present invention is put
Electricity reaction ionised isotopes mass spectrograph (RFRIS-IRMS), corollary equipment is accelerated solvent extraction (Dai An companies of the U.S., model
ASE200), including testing procedure is as follows：
A, extraction process-accelerated solvent extraction
Pedotheque is crushed to 100 mesh or so, loads abstraction pool, using dichloromethane/acetone (5：1) extracted,
Detailed extraction conditions is：Furnace temperature：100 DEG C, pressure：10.3Mpa the quiet hour：5min (after the pre- thermal balances of 5min), rinse body
Product：The 60% of abstraction pool volume, nitrogen cleaning：80s under 1.03Mpa pressure, quiescent period：2 times.The sample extracted is blown in nitrogen
Below 0.5ml is concentrated on instrument, then with normal hexane constant volume to 1ml；
B, gas-chromatography separates：By the sample of said extracted, load gas chromatography system and separated, chromatographic condition is such as
Under：Capillary chromatographic column：DB-5MS (30m × 0.25mm × 0.25 μm) post, chromatographic program Elevated Temperature Conditions：50 DEG C of initial temperature,
0min is kept, then rises to 180 DEG C with 25 DEG C/min speed, then 300 DEG C are risen to 15 DEG C/min speed, keeps 3min；
Injector temperature：210℃；Input mode：Do not shunt；Sampling volume：1μl；
C, the component after chromatography is directly flowed into the reaction ionization tube of ion gun by tubing string, through radio frequency discharge field
Ionization, radio frequency operation voltage 12V, working frequency 75MHz；Reaction gas argon flow amount 50.0mL/min, supplement reaction gas nitrogen stream
50.0mL/min is measured, the bromine in organic matter decis is ionized in the above conditions, while is efficiently produced electronegative bromine and born
Ion (79Br-、81Br-), so that quality analysis uses；
D, caused by ionization79Br-、81Br-Compressed and deflected under the influence of a magnetic field after transmitting to source slit, so
Received afterwards by the Faraday cup that mass number is 79,81,79Br-、81Br-Ion stream intensity I79、I81It is calculated together by following formula
The plain ratio R in positionBr：
Finally by the R of above-mentioned result of calculationBrValue calculates compared with the similar standard substance of known isotopic standard value,
Draw final δ81Br values：
WhereinFor standard substance value.
Embodiment 4
The fingerprint analysis of chlorine isotope in reagent hexachloro-benzene, instrument are gas-chromatography radio frequency discharge of the present invention
Reaction ionised isotopes mass spectrograph (GC-RFRIS-IRMS), including testing procedure are as follows：
A, gas-chromatography separates：After hexachloro-benzene reagent is dissolved using normal hexane, load gas chromatography system and separated,
Chromatographic condition is as follows：Capillary chromatographic column：DB-5MS (30m × 0.25mm × 0.25 μm) post, chromatographic program Elevated Temperature Conditions：Initially
Temperature 50 C, 0min is kept, then rises to 180 DEG C with 25 DEG C/min speed, then 300 DEG C are risen to 15 DEG C/min speed,
Keep 3min；Injector temperature：210℃；Input mode：Do not shunt；Sampling volume：1μl；
C, the component after chromatography is directly flowed into the reaction ionization tube of ion gun by tubing string, through radio frequency discharge field
Ionization, radio frequency operation voltage 12V, working frequency 400MHz；Reaction gas helium gas flow 20.0mL/min, supplement reaction gas nitrogen stream
100.0mL/min is measured, organic matter hexachloro-benzene is ionized in the above conditions, while efficiently produces electronegative chlorine anion
(35Cl-、37Cl-)。
D, caused by ionization35Cl-、37Cl-Deflect under the influence of a magnetic field, then by the reception matter of isotope mass spectrometry
The Faraday cup that number is 35,37 is measured to receive35Cl-、37Cl-, output is finally amplified by signal detector, receives detection
Detect35Cl-、37Cl-, respective peak intensity, I37, I35And isotopic ratio R is calculated by following formulaCl：
Finally by the R of above-mentioned result of calculationClValue calculates compared with the similar standard substance of known isotopic standard value,
Calculation formula is as follows：
WhereinFor standard substance value.
Claims (10)
1. a kind of ion gun, including reaction ionization tube, induction coil, power amplifier and radio-frequency signal generator, reaction ionization
Pipe stage casing is induced coil and wrapped up, and the radio-frequency signal generator is of coupled connections with power amplifier, radio-frequency signal generator
Radiofrequency signal by signal after power amplifier be exaggerated strengthen and be transferred on induction coil, be internally formed in induction coil
Radiofrequency signal field, it is characterised in that：Also include two reaction gas inlet ducts, be respectively arranged at reaction ionization tube arrival end and
The port of export.
2. ion gun according to claim 1, it is characterised in that：The reaction ionization tube is by high temperature resistant quartz ampoule or ceramics
Material is made.
3. ion gun according to claim 2, it is characterised in that：The radio frequency range of the radio-frequency signal generator exists
Between 20-400MHz.
A kind of 4. new chlorine bromine isotope mass spectrometer, as the ion gun any one of claim 1-3 and capillary gas phase
Chromatographic system and magnetic substance spectra system coupling composition, the capillary column of the capillary gas chromatography system and the reaction electricity of ion gun
Arrival end from pipe connects, and the port of export for reacting ionization tube connects with magnetic substance spectra system, and wherein magnetic substance spectra system passes including ion
Defeated passage, magnetic substance contents analyzer, Faraday cup ion detection and signal output system and corresponding vacuum system.
5. new chlorine bromine isotope mass spectrometer according to claim 4, it is characterised in that：The capillary gas chromatography
The capillary column length range of system is between 30-60 rice, and higher than 3000 every meter, total number of plates reaches chromatographic column theoretical cam curve
105More than, the appearance time of different component is between 10-50s.
6. new chlorine bromine isotope mass spectrometer according to claim 4, it is characterised in that：The Faraday cup ion is visited
Survey and signal output system include Faraday cup detector and electron multiplier, the mass number that Faraday cup is received be (35,
37) or (79,81), the Faraday cup detector use the arrangement of 3 Faraday cups, and one of passage is shared by switching.
7. the new chlorine bromine isotope mass spectrometer according to any one of claim 4-6, it is characterised in that：The magnetic substance
Contents analyzer uses the magnetic field of 230mm radiuses, and magnetic field incident, outgoing border use 26.5 degree, and its theoretical abbe number is 920,
Source slit 0.3mm, receives slit 1.4mm, and mass resolution is more than 160.
8. a kind of chlorine or bromine isotopic ratio analysis method, specifically includes following steps：
A, the sample by chlorine or bromine for organic matter, load gas chromatography system and separated；
B, the component after chromatography directly by capillary column flow into ion gun reaction ionization tube in, reaction gas simultaneously from
React ionization tube arrival end import, object under the auxiliary of reaction gas, through radio frequency discharge react ionize, supplement reaction gas from
React ionization tube the port of export import, in the presence of reaction gas is supplemented, the chlorine or bromine in object formed pure chlorine bear from
Son or bromine anion, so that quality analysis uses；
C, chlorine or bromine anion enters magnetic substance contents analyzer through ion transmission channel, by Faraday cup ion after being deflected in magnetic field
Detection and signal output system receive detection.
9. chlorine or bromine isotopic ratio analysis method according to claim 8, it is characterised in that：The first via reaction gas
For helium or argon gas, range of flow 1.0-50.0mL/min.
10. chlorine or bromine isotopic ratio analysis method according to claim 9, it is characterised in that：The second tunnel reaction
Gas is nitrogen, range of flow 1.0-100.0mL/min.
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| CN201710510223.6A CN107464735A (en) | 2017-06-28 | 2017-06-28 | A kind of new chlorine bromine isotope mass spectrometer and its analysis method |
| PCT/CN2017/105329 WO2019000699A1 (en) | 2017-06-28 | 2017-10-09 | Novel chlorine/bromine isotope mass spectrometer and analysis method therefor |
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| CN113767281A (en) * | 2019-11-27 | 2021-12-07 | 昭和电工株式会社 | Method for measuring fluorine gas concentration in halogen-containing fluoride gas by mass spectrometer |
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| WO2009064561A1 (en) | 2007-11-12 | 2009-05-22 | Nielsen Media Research, Inc. | Methods and apparatus to perform audio watermarking and watermark detection and extraction |
| CN110763535B (en) * | 2019-10-31 | 2022-11-25 | 上海化工研究院有限公司 | Sample preparation method for measuring nitrite nitrogen 15 isotopic abundance |
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| CN113767281A (en) * | 2019-11-27 | 2021-12-07 | 昭和电工株式会社 | Method for measuring fluorine gas concentration in halogen-containing fluoride gas by mass spectrometer |
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| WO2019000699A1 (en) | 2019-01-03 |
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