Application of Dual Electron Impact-Chemical Ionization Ion Source to Gaschromatograph-Mass spectrometer

1976 ◽  
Vol 24 (1) ◽  
pp. 139-147
Author(s):  
MASAYA IWANAGA ◽  
KIYOSHI HOSOI ◽  
NORIO KAMESHIMA ◽  
SHOZO ONISHI
Keyword(s):  
Electron Impact ◽  
Mass Spectrometer ◽  
Chemical Ionization ◽  
Ion Source

scholarly journals Interaction of Fullerenes with Organosilanes in the Ionization Chamber of a Mass Spectrometer under Electron Impact and the Reaction of C60with Tetraphenylsilane in Solution under UV Irradiation

2016 ◽  
Vol 2016 ◽  
pp. 1-9
Author(s):  
Yury I. Lyakhovetsky ◽  
Elena A. Shilova ◽  
Alexandra P. Pleshkova ◽  
Alexander I. Belokon ◽  
Sergey O. Yakushin ◽  
...  
Keyword(s):  
Electron Impact ◽  
Mass Spectrometer ◽  
Uv Irradiation ◽  
Ionization Chamber ◽  
Ion Source ◽  
Organic Radicals ◽  
Mechanistic Study ◽  
Mass Spectral ◽  
Additional Support ◽  
Derivatives Of

C60was shown to react with organosilanes Me4Si, Ph2SiH2, Ph2MeSiH, Ph4Si, andα-naphthylphenylmethylsilane in the electron ionization ion source of a mass spectrometer with the transfer of the corresponding organic radicals (Me, Ph, andα-naphthyl) from the silanes to the fullerene. The reactions were accompanied by hydrogen addition to some products and hydrogen loss from them. C70reacted with Me4Si analogously. A reaction mechanism involving homolytic dissociation of the silanes under electron impact to the corresponding organic radicals, which react further with C60at the surface of the ionization chamber of the mass spectrometer to give the respective adducts, was offered. A mechanistic study of the reaction of C60with Me4Si supported it. No silicon containing derivatives of the fullerenes were found. C60reacted with Ph4Si in solution under UV irradiation in a similar fashion furnishing phenyl derivatives of the fullerene. These results provide an additional support to the hypothesis formulated earlier thatthe homolytic reactive mass spectrometry of fullerenes (the reactions of fullerenes with other species in the ionization chambers of mass spectrometers and their mass spectral monitoring)can predict the reactivity of them toward the same reagents in solution to a significant extent.

scholarly journals Characterization of the mass-dependent transmission efficiency of a CIMS

2016 ◽  
Vol 9 (4) ◽  
pp. 1449-1460 ◽  
Author(s):  
Martin Heinritzi ◽  
Mario Simon ◽  
Gerhard Steiner ◽  
Andrea C. Wagner ◽  
Andreas Kürten ◽  
...  
Keyword(s):  
Mass Spectrometer ◽  
Chemical Ionization ◽  
Transmission Efficiency ◽  
Ion Source ◽  
Mass Discrimination ◽  
Perfluorinated Acids ◽  
Relative Transmission ◽  
The Absolute ◽  
Primary Ions

Abstract. Knowledge about mass discrimination effects in a chemical ionization mass spectrometer (CIMS) is crucial for quantifying, e.g., the recently discovered extremely low volatile organic compounds (ELVOCs) and other compounds for which no calibration standard exists so far. Here, we present a simple way of estimating mass discrimination effects of a nitrate-based chemical ionization atmospheric pressure interface time-of-flight (CI-APi-TOF) mass spectrometer. Characterization of the mass discrimination is achieved by adding different perfluorinated acids to the mass spectrometer in amounts sufficient to deplete the primary ions significantly. The relative transmission efficiency can then be determined by comparing the decrease of signals from the primary ions and the increase of signals from the perfluorinated acids at higher masses. This method is in use already for PTR-MS; however, its application to a CI-APi-TOF brings additional difficulties, namely clustering and fragmentation of the measured compounds, which can be treated with statistical analysis of the measured data, leading to self-consistent results. We also compare this method to a transmission estimation obtained with a setup using an electrospray ion source, a high-resolution differential mobility analyzer and an electrometer, which estimates the transmission of the instrument without the CI source. Both methods give different transmission curves, indicating non-negligible mass discrimination effects of the CI source. The absolute transmission of the instrument without the CI source was estimated with the HR-DMA method to plateau between the m∕z range of 127 and 568 Th at around 1.5 %; however, for the CI source included, the depletion method showed a steady increase in relative transmission efficiency from the m∕z range of the primary ion (mainly at 62 Th) to around 550 Th by a factor of around 5. The main advantages of the depletion method are that the instrument is used in the same operation mode as during standard measurements and no knowledge of the absolute amount of the measured substance is necessary, which results in a simple setup.

1,1',3,3'-Tetramethyl-5-(4-methylamino-3-nitrobenzyl)-5,5'-methylenebisbarbituric acid

1976 ◽  
Vol 29 (10) ◽  
pp. 2219 ◽  
Author(s):  
JW Clark-Lewis ◽  
GL Aldous ◽  
MJ Thompson
Keyword(s):  
Electron Impact ◽  
Mass Spectrometer ◽  
Chemical Ionization ◽  
Barbituric Acid ◽  
Mass Spectrometric ◽  
Negative Ion ◽  
Spectroscopic Methods ◽  
Thermal Fragmentation ◽  
Related Compounds

The previously proposed structure (2) for the compound named in the title is confirmed by spectroscopic methods and by synthesis of related compounds. The barbituric acid undergoes a very facile thermal fragmentation in the mass spectrometer into 1,3-dimethyl-5-(4-ethylamino-3-nitrobenzy1)-barbituric acid (3) (which was also prepared by unambiguous synthesis) and 1,3-dimethyl-5-methylenebarbituric acid (4). The electron-impact, chemical-ionization, and negative-ion mass spectrometric behaviour of the barbituric acid (2) was examined.

scholarly journals The airborne mass spectrometer AIMS – Part 2: Measurements of trace gases with stratospheric or tropospheric origin in the UTLS

2015 ◽  
Vol 8 (12) ◽  
pp. 13567-13607 ◽  
Author(s):  
T. Jurkat ◽  
S. Kaufmann ◽  
C. Voigt ◽  
D. Schäuble ◽  
P. Jeßberger ◽  
...  
Keyword(s):  
Nitrogen Oxide ◽  
Mass Spectrometer ◽  
Chemical Ionization ◽  
Trace Gases ◽  
Measurement Techniques ◽  
Ion Source ◽  
Trace Gas ◽  
Ionization Mass ◽  
Custom Made ◽  
Gas Measurements

Abstract. Understanding the role of climate-sensitive trace gas variabilities in the upper troposphere and lower stratosphere region (UTLS) and their impact on its radiative budget requires accurate measurements. The composition of the UTLS is governed by transport and chemistry of stratospheric and tropospheric constituents, such as chlorine, nitrogen oxide and sulphur components. The Airborne chemical Ionization Mass Spectrometer AIMS has been developed to accurately measure a set of these constituents on aircraft by means of chemical ionization. Here we present a setup using chemical ionization with SF5− reagent ions for the simultaneous measurement of trace gas concentrations in the pptv to ppmv (10−12 to 10−6 mol mol−1) range of HCl, HNO3 and SO2 with in-flight and online calibration called AIMS-TG. Part 1 of this paper (Kaufmann et al., 2015) reports on the UTLS water vapour measurements with the AIMS-H2O configuration. The instrument can be flexibly switched between two configurations depending on the scientific objective of the mission. For AIMS-TG, a custom-made gas discharge ion source has been developed generating a characteristic ionization scheme. HNO3 and HCl are routinely calibrated in-flight using permeation devices, SO2 is permanently calibrated during flight adding an isotopically labelled 34SO2 standard. In addition, we report on trace gas measurements of HONO which is sensitive to the reaction with SF5−. The detection limit for the various trace gases is in the low ten pptv range at a 1 s time resolution with an overall uncertainty of the measurement in the order of 20 %. AIMS has been integrated and successfully operated on the DLR research aircraft Falcon and HALO. Exemplarily, measurements conducted during the TACTS/ESMVal mission with HALO in 2012 are presented, focusing on a classification of tropospheric and stratospheric influences in the UTLS region. Comparison of AIMS measurements with other measurement techniques allow to draw a comprehensive picture of the sulphur, chlorine and reactive nitrogen oxide budget in the UTLS. The combination of the trace gases measured with AIMS exhibit the potential to gain a better understanding of the trace gas origin and variability at and near the tropopause.

scholarly journals The airborne mass spectrometer AIMS – Part 2: Measurements of trace gases with stratospheric or tropospheric origin in the UTLS

2016 ◽  
Vol 9 (4) ◽  
pp. 1907-1923 ◽  
Author(s):  
Tina Jurkat ◽  
Stefan Kaufmann ◽  
Christiane Voigt ◽  
Dominik Schäuble ◽  
Philipp Jeßberger ◽  
...  
Keyword(s):  
Nitrogen Oxide ◽  
Mass Spectrometer ◽  
Chemical Ionization ◽  
Trace Gases ◽  
Measurement Techniques ◽  
Ion Source ◽  
Trace Gas ◽  
Ionization Mass ◽  
Custom Made ◽  
Research Aircraft

Abstract. Understanding the role of climate-sensitive trace gas variabilities in the upper troposphere and lower stratosphere region (UTLS) and their impact on its radiative budget requires accurate measurements. The composition of the UTLS is governed by transport and chemistry of stratospheric and tropospheric constituents, such as chlorine, nitrogen oxide and sulfur compounds. The Atmospheric chemical Ionization Mass Spectrometer AIMS has been developed to accurately measure a set of these constituents on aircraft by means of chemical ionization. Here we present a setup using SF5− reagent ions for the simultaneous measurement of trace gas concentrations of HCl, HNO3 and SO2 in the  pptv to ppmv (10−12 to 10−6 mol mol−1) range with in-flight and online calibration called AIMS-TG (Atmospheric chemical Ionization Mass Spectrometer for measurements of trace gases). Part 1 of this paper (Kaufmann et al., 2016) reports on the UTLS water vapor measurements with the AIMS-H2O configuration. The instrument can be flexibly switched between two configurations depending on the scientific objective of the mission. For AIMS-TG, a custom-made gas discharge ion source has been developed for generation of reagent ions that selectively react with HCl, HNO3, SO2 and HONO. HNO3 and HCl are routinely calibrated in-flight using permeation devices; SO2 is continuously calibrated during flight adding an isotopically labeled 34SO2 standard. In addition, we report on trace gas measurements of HONO, which is sensitive to the reaction with SF5−. The detection limit for the various trace gases is in the low 10 pptv range at a 1 s time resolution with an overall uncertainty of the measurement of the order of 20 %. AIMS has been integrated and successfully operated on the DLR research aircraft Falcon and HALO (High Altitude LOng range research aircraft). As an example, measurements conducted during the TACTS/ESMVal (Transport and Composition of the LMS/UT and Earth System Model Validation) mission with HALO in 2012 are presented, focusing on a classification of tropospheric and stratospheric influences in the UTLS region. The combination of AIMS measurements with other measurement techniques yields a comprehensive picture of the sulfur, chlorine and reactive nitrogen oxide budget in the UTLS. The different trace gases measured with AIMS exhibit the potential to gain a better understanding of the trace gas origin and variability at and near the tropopause.

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